Diurethanes

ABSTRACT

New and valuable diurethanes having a good herbicidal action, herbicides containing these compounds, and a process for controlling the growth of unwanted plants with these compounds.

This is a continuation of application Ser. No. 869,323 filed Jan. 13, 1978, now U.S. Pat. No. 4,227,007.

The present invention relates to new and valuable diurethanes having a herbicidal action, herbicides containing these compounds, and a process for controlling the growth of unwanted plants with these compounds.

It is known to use 2-sec-butyl-4,6-dinitrophenol (U.S. Pat. No. 2,192,197), ethyl-N-(3-N'-phenylcarbamoyloxy)-phenyl)-carbamate and methyl-N-(3-(N'-(3'-methylphenylcarbamoyloxy)-phenyl)-carbamate (German Printed Application DAS No. 1,567,151), 3-isopropyl-2,1,3-benzothiadiazin-(4)-one-2,2-dioxide (German Printed application DAS No. 1,542,836), and 1-phenyl-4-amino-5-chloropyridazone-(6) (German Pat. No. 1,105,232) as herbicides. These compounds are established herbicides with special areas of application.

We have now found that new diurethanes of the formula ##STR1## where R¹ and R² are identical or different and each denotes hydrogen, alkyl (e.g., methyl, ethyl, isopropyl), alkoxyalkyl (e.g., methoxymethyl, 2-methoxyethyl), haloalkyl (e.g., chloromethyl), unsubstituted benzyl, or benzyl substituted by alkyl or halogen, R³ and R⁴ are identical or different and each denotes unsubstituted alkyl, alkyl substituted by halogen, alkoxy or substituted or unsubstituted aryl (e.g., methyl, ethyl, 2-chloroethyl, 2-methoxyethyl, benzyl, isopropyl, n-propyl, 4-chlorobenzyl, n-butyl, sec.-butyl, tert.-butyl, isobutyl, 2,4-dichlorobenzyl, 2-ethylhexyl, n-decyl), unsubstituted or halogen-substituted alkenyl (e.g., allyl, 2-chloropropen-(1)-yl-(3), buten-(1)-yl-(3)), unsubstituted or halogen- or alkoxy-substituted alkynyl (e.g., propargyl, butyn-(1)-yl-(3), 1-chlorobutyn-(2)-yl-(4), unsubstituted or alkyl-substituted cycloalkyl (e.g. cyclopentyl, cyclohexyl, 3-methylcyclohexyl, 2,6-dimethylcyclohexyl, cycloheptyl, 4-tert.-butylcyclohexyl, cyclooctyl, cyclododecyl, 3,5-dimethylcyclohexyl), bicycloalkyl (e.g., norbornyl), tricycloalkyl (e.g., tricyclo-[4,3,1²,5 0¹,6 ]-decyl), phenyl with fused ring system (e.g., naphthyl, benzofuranyl, indyl), phenyl, mono- or polysubstituted phenyl with the substituents alkyl, haloalkyl, alkoxyalkyl, cycloalkyl, halogen, alkoxy, haloalkoxy, alkoxycarbonylalkoxy, nitro, amino, aryl, aryloxy, thiocyanato, cyano, ##STR2## (e.g., phenyl, 4-fluorophenyl, 2-methoxyphenyl, 3-methylphenyl, 2-fluorophenyl, 3-methyl-5-isopropylphenyl, 3-ethylphenyl, 3-chlorophenyl, 2,4,6-trimethylphenyl, 3-fluorophenyl, 3-chloro-4-fluorophenyl, 3,4-dimethylphenyl, 3-trifluoromethylphenyl, 4-methylphenyl, 3,4-difluorophenyl, 3-chloro-4-methylphenyl, 3-bromophenyl, 4-iodophenyl, 4-chlorophenyl, 2-chlorophenyl, 2-chloro-4-fluorophenyl, 3-isopropylphenyl, 4-ethylphenyl, 3-methoxycarbonylaminophenyl, 4-ethoxyphenyl, 2-methylphenyl, 3-methoxyphenyl, 4-cyanophenyl, 2,6-dimethylphenyl, 2,4-dichlorophenyl, 3-methyl-4-chlorophenyl, 2-trifluoromethylphenyl, 2,4-dibromophenyl, 4-trifluoromethylphenyl, 4-methoxyphenyl, and 3-(1'-ethoxycarbonylethoxy)-phenyl), R⁵ and R⁶ being identical or different and each denoting hydrogen, unsubstituted or mono- or polysubstituted aryl, or one of the two substituents having the meanings given for R¹, and W, X, Y and Z are identical or different and each denotes hydrogen, alkyl (e.g., methyl), haloalkyl (e.g., trifluoromethyl), alkoxy (e.g., methoxy), halogen (fluoro, chloro, bromo, iodo), nitro or amino, have a good herbicidal action on numerous unwanted plants and are well tolerated by many crop plants. The new compounds also have a fungicidal action.

The new compounds may for example be prepared by the following methods; the radicals W, X, Y, Z, R¹, R², R³ and R⁴ have the above meanings. ##STR3##

This reaction scheme clearly illustrates the interrelationship between the starting materials. It is also clear that, depending on the nature of the substituents W, X, Y, Z, R¹, R², R³ and R⁴ and on the availability of the reactants, one route or another may be advantageous. The reaction of F to give H is preferred.

Starting from prior art meta-nitroanilines (A), meta-nitrophenyl isocyanates (B) may be prepared (W. Siefkin, J. Liebigs Annalen der Chemie, 562, 75 et seq., 1949) which in turn react smoothly with the hydroxy components R³ --OH to give the nitrourethanes (C) (S. Petersen, Methoden der Organ. Chemie, VIII, 131, Georg-Thieme-Verlag, Stuttgart, 4th ed., 1952), which are, however, also accessible direct from the meta-nitroanilines (A) and chloroformates (R³ O--CO--Cl) (German Laid-Open Application DOS No. 1,643,763). Subsequent reduction gives the amino compounds (F; R² ═H) (S. Schroter, Methoden der Organ. Chemie, XI/1, 360 et seq., Georg-Thieme-Verlag, Stuttgart, 4th ed., 1957) which are reacted, either direct or after conversion into the product mono-substituted on the amino nitrogen (F; R² ≠H) (Methoden der Organ. Chemie, XI/1, 24 et seq., Georg-Thieme-Verlag, Stuttgart, 4th ed., 1957) with chloroformates (R⁴ O--CO--Cl), to give the desired diurethanes (H) (German Laid-Open Application DOS No. 1,643,763). The aminourethanes (F) may also be obtained by reaction of meta-phenylenediamines (D) with chloroformates. A further synthesis possibility is the reaction of aryl-1,3-diisocyanates (E) with only 1 mole of the hydroxy component R³ --OH; this reaction gives the isocyanatourethanes (G) (J. A. Parker, J. J. Thomas and C. L. Zeise, J. Org. Chem., 22, 594-596, 1957), which are also obtainable by phosgenating the aminourethanes (F) (German Laid-Open application DOS No. 1,914,270, p. 5, Ex. 8). Subsequent reaction with the hydroxyl component R⁴ OH gives the desired end products. In principle, the --COOR³ or --COOR⁴ groupings may be introduced in any order.

The preferred synthesis stages are described in more detail below:

(a) The 3-nitrophenyl isocyanates (B) are reacted with or without a catalyst usually used for isocyanate reactions, e.g., tertiary amines (triethylamine, 1,4-diazabicyclo-(2,2,2)-octane), nitrogenous heterocycles (pyridine, 1,2-dimethylimidazole) or organic tin compounds (dibutyl tin diacetate, dimethyl tin dichloride), in the presence or absence of a solvent inert under the reaction conditions, e.g., hydrocarbons (ligroin, naphtha, toluene, pentane, cyclohexane), halohydrocarbons (methylene chloride, chloroform, dichloroethane, chlorobenzene, o-, m- and p-dichlorobenzene), nitrohydrocarbons (nitrobenzene, nitromethane), nitriles (acetonitrile, butyronitrile, benzonitrile), ethers (diethyl ether, tetrahydrofuran, dioxane), esters (ethyl acetate, methyl propionate), ketones (acetone, methyl ethyl ketone) or amides (dimethylformamide, formamide) (German Laid-Open application DOS No. 1,568,138), at temperatures of from 0° to 150° C., preferably from 40° to 100° C.

(b) 3-nitroanilines (A) are reacted with a chloroformate in a suitable solvent, e.g., water, alcohols (methanol, ethanol, isopropanol) or those given under (a), with the additional employment of a conventional acid binder, e.g., alkali metal hydroxides, carbonates, bicarbonates, alkaline earth metal oxides, hydroxides, carbonates, bicarbonates, and tertiary organic bases (e.g., triethylamine, pyridine, N,N-dimethylaniline, N,N-dimethylcyclohexylamine, quinoline, tributylamine) or starting material 3-nitroaniline, at temperatures of from -20° to +150° C., preferably from +20° to 80° C.

(c) The nitrourethanes (C) may be reduced by one of the prior art processes, e.g., by catalytic hydrogenation, by a metal/acid combination, e.g., a combination of iron and acid, by a metal/alcohol combination, e.g., zinc dust/aqueous alcohol, iron/aqueous alcohol, etc.

(d) For the reaction of the m-phenylenediamines (D), comparable conditions as for (b) apply; it may, however, be advantageous to employ an excess of m-phenylenediamine.

(e) The aminourethanes F are reacted with chloroformates analogously to (b); the solution obtained for example by catalytic hydrogenation of the nitrourethanes C may also be employed direct without further purification.

The preparation of the new diurethanes and their precursors is illustrated by the following examples.

I NITROURETHANES

EXAMPLE A

At 20° to 25° C. and while stirring, a mixture of 85 parts by weight of 3-nitrophenyl isocyanate and 43 parts by weight of toluene (absolute) is metered into a solution of 64.3 parts by weight of 4-chlorophenol and 3 parts by weight of triethylamine in 430 parts by weight of toluene (absolute).

To complete the reaction, the mixture was stirred for 1 hour at room temperature. After cooling to 0° C., the reaction product was suction filtered; m.p.: 137°-138° C.

The compound has the following structural formula: ##STR4##

EXAMPLE B

17.4 parts of sodium bicarbonate is added to 26 parts by weight of 3-nitro-N-methylaniline in 320 parts by weight of ethyl acetate. While stirring, 33 parts by weight of m-tolyl chloroformate is slowly added, the mixture is stirred for 20 hours at room temperature and filtered, the solvent is removed in vacuo, and the residue which remains is recrystallized from toluene/cyclohexane; m.p.: 114°-116° C.

The compound has the following structural formula: ##STR5##

The following nitrourethanes (C) may be prepared analogously:

    __________________________________________________________________________      ##STR6##                                                                      W  X   Y  Z  R.sup.1                                                                               R.sup.3       m.p. °C.                              __________________________________________________________________________     H  H   H  H  H      4-fluorophenyl                                                                               116-167                                      H  H   H  H  H      2,4-dichlorophenyl                                         H  H   H  H  H      methyl        153-155                                      H  CH.sub.3                                                                           H  H  H      methyl        132-133                                      H  H   H  H  benzyl 4-chlorophenyl                                             H  H   H  H  H      phenyl        123-125                                      H  H   H  H  H      3-methoxyphenyl                                            H  H   H  H  CH.sub.3                                                                              phenyl        69-70                                        H  H   H  H  H      2-fluorophenyl                                                                               145-146                                      H  F   H  H  H      phenyl        138-140                                      H  H   H  H  H      3-bromophenyl 138                                          H  H   H  H  CH.sub.3 OCH.sub.2                                                                    3-methylphenyl                                             H  H   H  H  H      3,4-dimethylphenyl                                                                           130-131                                      H  H   CH.sub.3                                                                          H  H      methyl        86-87                                        H  H   H  H  H      4-methoxyphenyl                                                                              132-133                                      H  CH.sub.3                                                                           H  H  H      ethyl         131-133                                      H  H   H  H  H      3-fluorophenyl                                                                               128-130                                      H  H   H  H  H      ethyl         64-66                                        CH.sub.3                                                                          H   H  H  H      phenyl        112-114                                      H  H   H  H  H      2-chloro-4-fluorophenyl                                                                      146-147                                      H  H   H  H  H      2-chlorophenyl                                                                               136-138                                      H  F   H  F  H      methyl                                                     H  H   H  H  C.sub.2 H.sub.5                                                                       4-cyanophenyl                                              H  H   H  CH.sub.3                                                                          H      methyl        114-117                                      H  H   H  H  H      3-trifluoromethylphenyl                                                                      119-120                                      Cl H   Cl H  CH.sub.3                                                                              2-methoxyethyl                                             H  H   H  H  H      4-trifluoromethylphenyl                                    H  H   H  H  CH.sub.3                                                                              cyclododecyl                                               H  H   H  H  H      4-ethylphenyl 86-88                                        H  H   H  Cl H      phenyl        125-127                                      H  H   H  H  H      3-chloro-4-fluorophenyl                                    H  CH.sub.3                                                                           H  H  4-methyl-                                                                             methyl                                                                  benzyl                                                            H  H   H  H  H      2,4,6-trimethylphenyl                                                                        212-213                                      H  H   H  Cl H      methyl        122-124                                      H  H   H  H  H      3,4-difluorophenyl                                         H  NO.sub.2                                                                           H  H  C.sub.2 H.sub.5                                                                       2,5-dichlorobenzyl                                         H  H   H  H  H                                                                                      ##STR7##     171-173                                      H  H   H  CH.sub.3                                                                          H      ethyl         80-81                                        H  H   H  H  H      cyclododecyl                                               H  H   H  H  H      3-isopropylphenyl                                                                            85-87                                        H  H   H  H  C.sub.2 H.sub.5 OCH.sub.2                                                             n-butyl                                                    H  H   H  H  H      2-trifluoromethylphenyl                                    H  H   H  H  H      cyclooctyl    103-105                                      H  H   H  H  H      4-methylphenyl                                                                               138-139                                      H  H   H  H  H      2,4-dibromophenyl                                          H  H   H  H  H      tert.-butyl   97-99                                        H  H   H  H  H      4-ethoxyphenyl                                             H  H   H  H  H      3-ethylphenyl 85-86                                        H  H   H  H  CH.sub.3                                                                              cycloheptyl                                                H  H   H  H  H      2,6-dimethylphenyl                                                                           165-167                                      H  H   CF.sub.3                                                                          H  H      isopropyl     121-123                                      H  F   H  H  H      4-difluoromethoxyphenyl                                    H  H   H  H  H      3-methoxycarbonyl-                                                                           172-174                                                          aminophenyl                                                H  H   H  H  H      2-methoxyphenyl                                            H  H   H  H  H      tricyclo-[4,3,1.sup.2,5 0.sup.1,6 ]-                                                         103-105                                                          decyl                                                      H  H   H  H  H      2-methylphenyl                                                                               126-128                                      H  H   H  H  H      4-iodophenyl                                               H  H   H  H  CH.sub.3                                                                              methyl        54-56                                        H  Cl  H  Cl H      2-cyclohexylphenyl                                         H  H   H  H  H      3-methyl-4-chlorophenyl                                    H  H   H  H  H      3,5-dimethylcyclohexyl                                     H  H   H  H  H      1-naphthyl    141-142                                      H  H   H  H  H      isopropyl     86-88                                        H  Br  H  H  H      ethyl                                                      H  H   H  H  H      4-nitrophenyl                                              H  F   H  H  H      methyl        116-118                                      CH.sub.3                                                                          H   H  H  benzyl ethyl                                                      H  H   CF.sub.3                                                                          H  H      phenyl        133-135                                      H  H   H  Br CH.sub.3                                                                              methyl                                                     H  H   H  H  H      2,6-dimethylcyclohexyl                                                                       121-123                                      H  H   H  H  CH.sub.3 OCH.sub.3                                                                    3-fluorophenyl                                             H  OCH.sub.3                                                                          H  H  H      methyl        131-132                                      CH.sub.3                                                                          H   H  H  CH.sub.3                                                                              benzyl                                                     H  H   CF.sub.3                                                                          H  CH.sub.3                                                                              phenyl                                                     H  H   H  H  H      cycloheptyl   102-104                                      H  H   H  H  H      benzyl        113-115                                      H  NO.sub.2                                                                           H  CH.sub.3                                                                          H      methyl                                                     H  OCH.sub.3                                                                          H  H  H      phenyl        209-211                                      H  H   H  H  H      3-methyl-5-isopropyl-                                                          phenyl                                                     H  H   H  H  benzyl n-butyl                                                    H  H   H  H  H      norbornyl     118-120                                      H  H   H  H  H      2-naphthyl                                                 H  H   NO.sub.2                                                                          H  C.sub.2 H.sub.5                                                                       3-methylphenyl                                             H  H   H  H  H      cyclopentyl   110-112                                      H  Cl  H  H  H      methyl        136-138                                      H  H   H  H  iso-   4-methylthiophenyl                                                      propyl                                                            H  H   H  H  H      3-methylcyclohexyl                                                                           120-122                                      H  H   H  H  H      cyclohexyl    117-118                                      H  H   H  H  H      2-methylcyclohexyl                                                                           100-102                                      H  H   H  H  H      1,3-dimethoxyisopropyl                                                                       95-96                                        H  H   H  H  H      3(N,N-dimethylamino)-                                                                        126-127                                                          phenyl                                                     H  H   H  H  H      3,4-(tetramethylene)-                                                                        164-166                                                          phenyl                                                     H  H   H  H  C.sub.2 H.sub.5                                                                       phenyl        56-58                                        H  H   H  H  H      hexahydrobenzyl                                                                              127-128                                      H  H   H  H  H      3,3,5-trimethylcyclo-                                                                        79-82                                                            hexyl                                                      H  H   H  H  H      3-methyl-5-ethylphenyl                                                                       115-117                                      H  H   H  H  H      tert-amyl     62-63                                        H  H   H  H  H      2,3,6-trimethylphenyl                                                                        180-182                                      H  H   H  H  H      2,3,5,6-tetramethyl-                                                                         237-238                                                          phenyl                                                     H  H   H  H  H      4-tert-butylphenyl                                                                           113-115                                      H  H   H  H  H      2,3,5-trimethylphenyl                                                                        145-147                                      H  H   H  H  H      2-isopropyl-5-methyl-                                                                        103-105                                                          phenyl                                                     H  H   H  H  H      2-tert-butyl-4-methyl-                                                                       154-156                                                          phenyl                                                     H  H   H  H  H      2,6-dimethoxyphenyl                                                                          155-157                                      H  H   H  H  H      3-methylphenyl                                                                               106-108                                      H  H   H  H  C.sub.2 H.sub.5                                                                       3-methylphenyl                                                                               75-77                                        H  H   H  H  H      2-methyl-6-isopropyl                                                                         122-124                                      H  H   H  H  H      3,5-diethylphenyl                                                                            128-130                                      __________________________________________________________________________

II AMINOURETHANES

EXAMPLE C

3 parts of a hydrogenation catalyst (palladium on animal charcoal, 10%) was added to a solution of 135 parts by weight of 4-chlorophenyl N-(3-nitrophenyl)-carbamate in 900 parts by weight of tetrahydrofuran (absolute), and the mixture hydrogenated at room temperature and under a hydrogen pressure of 0.02 bar until the pressure no longer changes. The solution was freed from catalyst and dried with MgSO₄, and the solvent removed to such an extent that the crystalline reaction product was readily able to be suction filtered; m.p.: 186°-187° C.

Structure: ##STR8##

EXAMPLE D

While stirring vigorously, 25.2 parts by weight of phenyl chloroformate was very slowly dripped into a solution of 108 parts by weight of m-phenylene diamine in 1,000 parts by weight of water. After the reaction was over, the mixture was suction filtered, the solid washed several times with dilute hydrochloric acid, and the combined acidic solutions were neutralized with ammonia and suction filtered. The dry product thus obtained melts with decomposition at 178°-180° C. Structure: ##STR9##

EXAMPLE E

While stirring vigorously, 130 parts by weight of 3-(O-phenylcarbamoyl)-nitrobenzene is added to a mixture, heated to 80° C., of 110 parts by weight of iron powder, 240 parts by weight of alcohol, 160 parts by weight of water and 7 parts by weight of concentrated hydrochloric acid in such portions that the temperature is kept at 80° C. without additional heating. The mixture is then refluxed for 1 hour and suction filtered while hot, the residue is digested with about 2,000 parts by weight of acetone, and twice the amount of water is added to the combined filtrates before suction filtration is carried out; m.p. (after recrystallization from ethyl acetate): 180° C. (decomposes).

Structure: ##STR10##

EXAMPLE F

While stirring vigorously, 52.1 parts by weight of phenyl chloroformate is dripped slowly into 51 parts by weight of 2,4-diaminonitrobenzene and 43 parts by weight of sodium bicarbonate in 600 parts by weight of tetrahydrofuran. The mixture is stirred for 14 hours and then filtered, and the residue is washed with tetrahydrofuran. The solution is freed from solvent to such a degree that the crystalline crude product is readily able to be suction filtered. After washing with diethyl ether and drying, the substance melts at 223°-225° C. According to the nmr spectrum and ultimate analysis, it has the following structure: ##STR11##

The following aminourethanes (F) may be prepared analogously:

    __________________________________________________________________________      ##STR12##                                                                     W  X   Y  Z  R.sup.1                                                                               R.sup.3       m.p. °C.                              __________________________________________________________________________     H  H   H  H  H      4-fluorophenyl                                                                               166-167                                      H  H   H  H  H      2,4-dichlorophenyl                                         H  H   H  H  H      methyl        87-89                                        H  CH.sub.3                                                                           H  H  H      methyl        not                                                                            isolated                                     H  H   H  H  benzyl 4-chlorophenyl                                             H  H   H  NO.sub.2                                                                          H      methyl        187-189                                      H  H   H  H  H      3-methoxyphenyl                                            H  H   H  H  CH.sub.3                                                                              phenyl        68-70                                        H  H   H  H  H      2-fluorophenyl                                                                               172-173                                      H  F   H  H  H      phenyl        not                                                                            isolated                                     H  H   H  H  H      3-bromophenyl                                              H  H   H  H  CH.sub.3 OCH.sub.2                                                                    3-methylphenyl                                             H  H   H  H  H      3,4-dimethylphenyl                                                                           155-157                                      H  H   CF.sub.3                                                                          H  H      methyl        not                                                                            isolated                                     H  H   H  H  H      4-methoxyphenyl                                                                              146-149                                      H  CH.sub.3                                                                           H  H  H      ethyl         not                                                                            isolated                                     H  H   H  H  H      3-fluorophenyl                                                                               decom-                                                                         position                                     H  H   H  H  H      ethyl         not                                                                            isolated                                     CH.sub.3                                                                          H   H  H  H      phenyl        131-133                                      H  H   H  H  H      2-chloro-4-fluorophenyl                                                                      decom-                                                                         position                                     H  H   H  H  H      2-chlorophenyl                                                                               decom-                                                                         position                                     H  F   H  F  H      methyl        not                                                                            isolated                                     H  H   H  H  C.sub.2 H.sub.5                                                                       4-Cyanophenyl                                              H  H   H  CH.sub.3                                                                          H      methyl        not                                                                            isolated                                     H  H   H  H  H      3-trifluoromethylphenyl                                                                      126-128                                      Cl H   Cl H  CH.sub.3                                                                              2-methoxyethyl                                             H  H   H  H  H      4-trifluoromethylphenyl                                    H  H   H  H  CH.sub.3                                                                              cyclododecyl                                               H  H   H  H  H      4-ethylphenyl 160-161                                      H  H   H  Cl H      phenyl        215-217                                      H  H   H  H  H      3-chloro-4-fluorophenyl                                    H  CH.sub.3                                                                           H  H  4-methyl-                                                                             methyl                                                                  benzyl                                                            H  H   H  H  H      2,4,6-trimethylphenyl                                                                        150-152                                      H  H   H  Cl H      methyl                                                     H  H   H  H  H      3,4-difluorophenyl                                         H  NO.sub.2                                                                           H  H  C.sub.2 H.sub.5                                                                       2,4-dichlorobenzyl                                         H  H   H  H  H                                                                                      ##STR13##    184-186                                      H  H   H  CH.sub.3                                                                          H      ethyl         not                                                                            isolated                                     H  H   H  H  H      cyclododecyl                                               H  H   H  H  H      3-isopropylphenyl                                                                            68-70                                        H  H   H  H  C.sub.2 H.sub.5 OCH.sub.2                                                             n-butyl                                                    H  H   H  H  H      2-trifluoromethylphenyl                                    H  H   H  H  H      cyclooctyl    77-79                                        H  H   H  H  H      4-methylphenyl                                                                               158-162                                      H  H   H  H  H      2,4-dibromophenyl                                          H  H   H  H  H      tert-butyl    109-110                                      H  H   H  H  H      4-ethoxyphenyl                                             H  H   H  H  H      3-ethylphenyl 112-114                                      H  H   H  H  CH.sub.3                                                                              cycloheptyl                                                H  H   H  H  H      2,6-dimethylphenyl                                                                           160-161                                      H  H   CF.sub.3                                                                          H  H      isopropyl     102-104                                      H  F   H  H  H      4-difluoromethoxyphenyl                                    H  H   H  H  H      3(O-methylcarbamoyl)-                                                                        149-151                                                          phenyl                                                     H  H   H  H  H      2-methoxyphenyl                                            H  H   H  H  H      tricyclo-[4,3,1.sup.2,5 0.sup.1,6 ]-                                                         130-131                                                          decyl                                                      H  H   H  H  H      2-methylphenyl                                                                               170-172                                      H  H   H  H  H      4-iodophenyl                                               H  H   H  H  CH.sub.3                                                                              methyl        not                                                                            isolated                                     H  Cl  H  Cl H      2-cylcohexylphenyl                                         H  H   H  H  H      3-methyl-4-chlorophenyl                                    H  H   H  H  H      3,5-dimethylcyclohexyl                                     H  H   H  H  H      1-naphthyl    146-148                                      H  H   H  H  H      isopropyl     66-68                                        H  Br  H  H  H      ethyl                                                      H  H   H  H  H      4-nitrophenyl                                              H  F   H  H  H      methyl        not                                                                            isolated                                     CH.sub.3                                                                          H   H  H  benzyl ethyl                                                      H  H   CF.sub.3                                                                          H  H      phenyl        214-216                                      H  H   H  Br CH.sub.3                                                                              methyl                                                     H  H   H  H  H      2,6-dimethylcyclohexyl                                                                       not                                                                            isolated                                     H  H   H  H  CH.sub.3 OCH.sub.2                                                                    3-fluorophenyl                                             H  OCH.sub.3                                                                          H  H  H      methyl        not                                                                            isolated                                     CH.sub.3                                                                          H   H  H  CH.sub.3                                                                              benzyl                                                     H  H   CF.sub.3                                                                          H  CH.sub.3                                                                              phenyl                                                     H  H   H  H  H      cycloheptyl   86-88                                        H  H   H  H  H      benzyl        not                                                                            isolated                                     H  NO.sub.2                                                                           H  CH.sub.3                                                                          H      methyl                                                     H  OCH.sub.3                                                                          H  H  H      phenyl        84- 86                                       H  H   H  H  H      3-methyl-5-isopropyl-                                                                        not                                                              phenyl        isolated                                     H  H   H  H  benzyl n-butyl                                                    H  H   H  H  H      nornornyl     150-151                                      H  H   H  H  H      2-naphthyl                                                 H  H   NO.sub.2                                                                          H  C.sub.2 H.sub.5                                                                       3-methylphenyl                                             H  H   H  H  H      cyclopentyl   not                                                                            isolated                                     H  Cl  H  H  H      methyl        not                                                                            isolated                                     H  H   H  H  iso-   4-methylthiophenyl                                                      propyl                                                            H  H   H  H  H      3-methylcyclohexyl                                                                           95-97                                        H  H   H  H  CH.sub.3                                                                              3-methylphenyl                                                                               114-115                                      H  H   H  H  C.sub.2 H.sub.5                                                                       phenyl        104-106                                      H  H   H  H  C.sub.2 H.sub.5                                                                       3-methylphenyl                                                                               104-105                                      H  H   H  H  H      2-isopropyl-5-methyl-                                                                        122-123                                                          phenyl                                                     H  H   H  H  H      3-methylphenyl                                                                               142-144                                      H  H   H  H  H      2-tert-butyl-4-methyl-                                                                       89-91                                                            phenyl                                                     H  H   H  H  H      tert-amyl     65-67                                        H  H   H  H  H      hexahydrobenzyl                                                                              106-108                                      H  H   H  H  H      3,4-(tetramethylene)-                                                                        181-183                                                          phenyl                                                     H  H   H  H  H      3-methyl-5-ethylphenyl                                                                       102-104                                      H  H   H  H  H      4-tert-butylphenyl                                                                           175-177                                      H  H   H  H  H      2,3,5-trimethylphenyl                                                                        152-154                                      H  H   H  H  H      2,3,6-trimethylphenyl                                                                        155-156                                      H  H   H  H  H      3-(N,N-dimethylamine)-                                                                       132-133                                                          phenyl                                                     H  H   H  H  H      3,5-diethylphenyl                                                                            121-123                                      H  H   H  H  H      3,3,5-trimethylcyclo-                                                                         98-100                                                          hexyl                                                      H  H   H  H  H      cyclohexyl    122-124                                      H  H   H  H  H      2-methylcyclohexyl                                         H  H   H  H  H      1,3-dimethoxyisopropyl                                     H  H   H  H  H      2-methyl-6-isopropyl-                                                                        133-135                                                          phenyl                                                     __________________________________________________________________________      Note:                                                                          The amines termed "not isolated" were further reacted direct after             catalytic reduction without isolation and purification.                  

III DIURETHANES EXAMPLE 1

11 parts by weight of sodium bicarbonate was added to a solution of 18.7 parts by weight of 4-chlorophenyl N-(3-aminophenyl)-carbamate in 125 parts by weight of tetrahydrofuran (absolute); subsequently, 9.4 parts by weight of methyl chloroformate was metered in at 20° to 25° C. and while cooling. To complete the reaction, the mixture was stirred for 1 hour at room temperature, after which it was filtered and the residue was concentrated in vacuo. The oily residue was dissolved in a small amount of ether and crystallized by adding petroleum ether; m.p.: 166°-167° C. (No. 1).

The compound has the following structural formula: ##STR14##

The following compounds were prepared analogously:

    __________________________________________________________________________      ##STR15##                                                                     No. W  X   Y  Z   R.sup.1                                                                               R.sup.2                                                                               R.sup.3       R.sup.4    m.p.                  __________________________________________________________________________                                                              °C.            2   H  H   H  H   H      H      phenyl        methyl     162-164               3   H  Cl  H  H   H      H      methyl        phenyl     133-135               4   H  H   H  H   H      H      2-fluorophenyl                                                                               ethyl      120-121               5   CH.sub.3                                                                          H   H  H   H      H      ethyl         phenyl     181-183               6   H  H   H  H   H      H      methyl        3-fluorophenyl                                                                            138-139               7   H  H   H  H   CH.sub.3                                                                              H      phenyl        methyl     142-143               8   H  H   H  H   H      H      4-fluorophenyl                                                                               methyl     154-155               9   H  H   H  Cl  H      H      phenyl        ethyl      147-149               10  H  H   H  H   H      CH.sub.3                                                                              ethyl         phenyl     150-152               11  H  H   H  H   H      H      ethyl         4-ethylphenyl                                                                             94-96                 12  H  H   H  H   H      H      2,6-dimethyl- allyl      100-103                                               cyclohexyl                                     13  H  H   H  H   CH.sub.3                                                                              H      3-methylphenyl                                                                               methyl     103-104               14  H  H   H  H   H      H      3-methoxycarbo-                                                                              methyl     188-190                                               nylaminophenyl                                 15  H  H   H  H   H      H      isobutyl      phenyl     137-140               16  H  Cl  H  H   H      H      methyl        3-methylphenyl                                                                            154-156               17  H  H   H  H   H      H      ethyl         2,4-dichlorophenyl               18  H  H   H  H   H      H      2-fluorophenyl                                                                               methyl     176-177               19  H  H   H  H   benzyl H      methyl        4-chlorophenyl                   20  CH.sub.3                                                                          H   H  H   H      H      phenyl        methyl     164-166               21  H  H   H  H   H      H      methyl        3-methoxyphenyl                  22  H  H   H  H   H      H      ethyl         3-fluorophenyl                                                                            131-132               23  H  H   H  H   H      H      phenyl        ethyl      152-153               24  H  H   H  H   H      H      3-bromophenyl methyl     168-170               25  H  H   H  H   H      CH.sub.3 OCH.sub.2                                                                    methyl        3-methylphenyl                   26  H  H   H  H   H      H      4-fluorophenyl                                                                               phenyl     161-164               27  H  H   H  H   H      H      2,4-dichlorophenyl                                                                           methyl     152-154               28  H  H   H  H   CH.sub.3                                                                              H      methyl        phenyl     oil                   29  H  H   H  H   H      H      4-methoxyphenyl                                                                              methyl     165-166               30  H  H   H  H   H      H      methyl        3-ethylphenyl                                                                             106-107               31  H  H   H  H   H      H      3-methoxyphenyl                                                                              ethyl                            32  H  H   H  H   H      H      phenyl        2-chloroethyl                                                                             118-120               33  H  H   H  H   H      H      ethyl         4-methoxyphenyl                                                                           142-143               34  H  H   H  H   H      H      methyl        3-(N,N-dimethyl-                                                                          169-171                                                             amino)-phenyl                    35  H  H   H  H   H      H      4-fluorophenyl                                                                               ethyl      129- 132              36  H  H   H  H   H      H      5-indanyl     ethyl      101-103               37  H  H   H  H   H      H      2-chlorophenyl                                                                               methyl     170-171               38  H  H   H  H   C.sub.2 H.sub.5                                                                       H      4-cyanophenyl methyl                           39  H  H   H  H   H      H      cyclopentyl   phenyl     158-160               40  Cl H   Cl H   CH.sub.3                                                                              H      2-methoxyethyl                                                                               1-naphthyl                       41  H  H   H  H   H      H      methyl        4-trifluoromethyl-                                                             phenyl                           42  H  H   H  H   H      H      2-methoxyethyl                                                                               4-fluorophenyl                                                                            95-97                 43  H  H   H  H   H      CH.sub.3                                                                              methyl        cyclododecyl                     44  H  H   H  H   H      H      phenyl        isopropyl  114-115               45  H  H   H  H   H      H      ethyl         2-chlorophenyl                                                                            134-135               46  H  H   H  H   H      H      4-methylphenyl                                                                               ethyl      110-112               47  H  H   H  H   H      H      3-(N,N-dimethyl-                                                                             ethyl                                                            amino)-phenyl                                  48  H  H   H  H   H      H      ethyl         3-bromophenyl                    49  H  H   H  H   H      H      3-chloro-4-fluoro-                                                                           methyl                                                           phenyl                                         50  H  H   H  H   H      H      ethyl         4-chlorophenyl                                                                            146-148               51  H  H   H  H   H      H      4-trifluoromethyl-                                                                           ethyl                                                            phenyl                                         52  H  CH.sub.3                                                                           H  H   H      4-methyl-                                                                             phenyl        methyl                                                    benzyl                                                53  H  H   H  Cl  H      H      methyl        4-methylthiophenyl               54  H  H   H  H   H      H      3-trifluoromethyl-                                                                           ethyl      113-115                                               phenyl                                         55  H  H   H  H   H      H      methyl        4-methylphenyl                                                                            187-189               56  H  H   H  H   H      H      3,4-difluorophenyl                                                                           ethyl                            57  H  NO.sub.2                                                                           H  H   C.sub.2 H.sub.5                                                                       H      2,4-dichlorobenzyl                                                                           methyl                           58  H  H   H  H   H      H      methyl        cyclododecyl                                                                              123-125               59  H  H   H  H   H      H      3-isopropylphenyl                                                                            ethyl      59-61                 60  H  H   H  H   H      H      5-indanyl     methyl     152-154               61  H  H   H  H   H      C.sub.2 H.sub.5 OCH.sub.2                                                             methyl        n-butyl                          62  H  H   H  H   H      H      cyclododecyl  phenyl                           63  H  H   H  H   H      H      3-trifluoromethyl-                                                                           methyl     137-139                                               phenyl                                         64  H  H   H  H   H      H      cyclooctyl    ethyl                            65  H  H   H  H   H      H      methyl        3,4-difluorophenyl               66  H  H   H  H   H      H      methyl        3-isopropylphenyl                                                                         61-63                 67  H  H   H  H   H      H      phenyl        cyclooctyl                       68  H  H   H  H   H      H      ethyl         3-ethylphenyl                                                                             oil                   69  H  H   H  H   H      H      3-chloro-4-fluoro-                                                                           ethyl                                                            phenyl                                         70  H  H   H  H   H      H      methyl        2,4-dibromophenyl                71  H  H   H  H   H      H      cyclopentyl   methyl     104-106               72  H  H   H  H   H      H      ethyl         cyclododecyl                     73  H  H   H  H   H      H      methyl        cyclooctyl oil                   74  H  H   H  H   H      H      3,4-dimethylphenyl                                                                           methyl     94-96                 75  H  OCH.sub.3                                                                          H  H   H      H      methyl        phenyl     139-140               76  H  H   H  H   H      H      2-chloro-4-fluoro-                                                                           ethyl      130-132                                               phenyl                                         77  H  H   H  H   H      H      methyl        2,6-dimethylcyclo-                                                                        110-112                                                             hexyl                            78  H  H   H  H   H      H      ethyl         2,4-dibromophenyl                79  H  H   H  H   H      H      ethyl         3,4-dimethylphenyl                                                                        152-154               80  H  H   H  H   H      H      2-trifluoromethyl-                                                                           methyl                                                           phenyl                                         81  H  H   H  H   H      H      4-nitrophenyl methyl                           82  H  H   H  H   H      H      cycloheptyl   methyl     117-119               83  H  H   H  NO.sub.2                                                                           H      H      methyl        phenyl     153-155               84  H  H   H  H   H      H      4-ethoxyphenyl                                                                               ethyl                            85  H  H   H  H   H      H      tert-butyl    methyl     116-118               86  H  H   H  H   CH.sub.3                                                                              H      cycloheptyl   propargyl                        87  H  H   H  H   H      H      methyl        2-chloro-4-fluoro-                                                                        170-172                                                             phenyl                           88  H  H   H  H   H      H      ethyl         2-trifluoromethyl-                                                             phenyl                           89  H  H   H  H   H      H      methyl        4-ethoxyphenyl                   90  H  H   H  H   H      H      norbornyl     methyl     110-112               91  H  H   H  H   H      H      ethyl         2,6-dimethylphenyl                                                                        118-120               92  H  H   H  H   H      H      2,4,6-trimethyl-                                                                             methyl     158-159                                               phenyl                                         93  H  H   H  NO.sub.2                                                                           H      H      phenyl        methyl     213-215               94  H  H   H  H   H      H      methyl        2,6-dimethylphenyl                                                                        133-134               95  H  H   H  H   H      H      4-ethylphenyl methyl     148-150               96  H  F   H  H   H      H      4-difluoromethoxy-                                                                           methyl                                                           phenyl                                         97  H  H   H  H   H      H      benzyl        phenyl     140-142               98  H  H   H  H   H      H      methyl        2-methoxyphenyl                                                                           155-157               99  H  H   H  H   H      H      phenyl        tert-butyl 158-160               100 H  H   H  H   H      H      tricyclo-     methyl                                                           [4,3,1.sup.2,5 0.sup.1,6 ]-                                                    decyl                                          101 H  H   H  H   H      H      2-methylphenyl                                                                               ethyl      114-115               102 H  H   H  H   H      H      ethyl         2,4,6-trimethyl-                                                                          120-124                                                             phenyl                           103 H  H   H  NO.sub.2                                                                           H      H      n-butyl       methyl                           104 H  H   H  H   H      H      ethyl         tricyclo-                                                                      [4,3,1.sup.2,5 0.sup.1,6 ]-                                                    decyl                            105 H  H   H  H   H      H      methyl        benzyl     108-110               106 H  H   H  H   H      H      methyl        4-iodophenyl                     107 H  H   H  H   H      H      2-methylphenyl                                                                               methyl     158-159               108 H  H   H  H   H      CH.sub.3                                                                              ethyl         3-methylphenyl                                                                            101-102               109 H  H   H  H   H      H      2-methoxyphenyl                                                                              ethyl                            110 H  H   H  H   H      H      tricyclo-     phenyl                                                           [4,3,1.sup.2,5 0.sup.1,6 ]-                                                    decyl                                          111 H  H   H  H   H      H      norbornyl     phenyl     190-192               112 H  H   H  H   H      H      ethyl         4-iodophenyl                     113 H  Cl  H  Cl  H      CH.sub.3                                                                              2-cyclohexylphenyl                                                                           methyl                           114 H  H   H  H   H      H      phenyl        n-propyl   159-161               115 H  H   H  H   H      H      methyl        3-methyl-4-chloro-                                                                        160-162                                                             phenyl                           116 H  F   H  F   H      H      phenyl        methyl     164-166               117 H  H   H  H   H      H      3,5-dimethylcyclo-                                                                           ethyl                                                            hexyl                                          118 H  H   H  F   H      H      phenyl        methyl     119-122               119 H  H   H  H   H      H      propargyl     phenyl     92-94                 120 H  H   H  H   H      H      methyl        1-naphthyl 174-175               121 H  Br  H  H   H      ClCH.sub.2                                                                            ethyl         phenyl                           122 H  H   H  H   H      H      3-methyl-5-iso-                                                                              methyl     63-65                                                 propylphenyl                                   123 H  H   H  H   H      H      methyl        3,5-dimethylcyclo-                                                                        112-119                                                             hexyl                            124 H  H   H  CH.sub.3                                                                           H      H      methyl        cyclohexyl 146-148               125 H  H   H  H   H      H      3-methyl-4-chloro-                                                                           ethyl                                                            phenyl                                         126 CH.sub.3                                                                          H   H  H   benzyl H      ethyl         cyclohexyl                       127 H  H   H  H   H      H      phenyl        allyl      90-93                 128 H  H   H  H   H      H      2-naphthyl    methyl                           129 H  H   H  Br  CH.sub.3                                                                              H      methyl        4-chlorobutyn-                                                                 2-yl-1                           130 H  F   H  H   H      H      phenyl        methyl     133-135               131 H  H   H  H   CH.sub.3 OCH.sub.2                                                                    H      3-fluorophenyl                                                                               methyl                           132 H  H   H  H   H      H      ethyl         3-chlorophenyl                                                                            109-112               133 H  H   H  F   H      H      ethyl         phenyl     163-165               134 H  H   H  H   H      H      3,5-dimethylcyclo-                                                                           phenyl                                                           hexyl                                          135 H  H   CF.sub.3                                                                          H   H      CH.sub.3                                                                              methyl        phenyl                           136 H  NO.sub.2                                                                           H  CH.sub.3                                                                           H      H      methyl        4-fluorophenyl                   137 CH.sub.3                                                                          H   H  H   CH.sub. 3                                                                             H      benzyl        propargyl                        138 H  H   H  H   H      H      phenyl        butyn-1-yl-3                                                                              117-119               139 H  H   H  H   CH.sub.3                                                                              H      3-methyl-5-iso-                                                                              methyl                                                           propylphenyl                                   140 H  CH.sub.3                                                                           H  H   H      H      3-methylphenyl                                                                               methyl     155-157               141 H  H   H  H   H      benzyl sec-butyl     n-butyl                          142 H  H   NO.sub.2                                                                          H   C.sub.2 H.sub.5                                                                       H      3-methylphenyl                                                                               allyl                            143 H  H   H  CH.sub.3                                                                           H      H      methyl        3-chlorophenyl                                                                            168-170               144 H  H   H  H   H      H      isopropyl     3-methylphenyl                                                                            oil                   145 H  H   H  H   iso-   H      4-methylthiophenyl                                                                           n-propyl                                           propyl                                                       146 H  F   H  F   H      H      3-thiocyanatophenyl                                                                          methyl                           147 H  H   H  H   H      H      sec-butyl     phenyl     117-119               148 H  H   H  H   H      H      methyl        3-aminophenyl                    149 H  CH.sub.3                                                                           H  H   H      H      methyl        3-chlorophenyl                                                                            105-107               150 H  H   H  H   H      H      diphenyl      methyl                           151 H  H   H  H   H      H      3(N',N'-dimethyl-                                                                            allyl                                                            ureido)-phenyl                                 152 H  CH.sub.3                                                                           H  H   H      H      methyl        phenyl     147-149               153 H  F   H  F   H      CH.sub.3                                                                              methyl        3-phenoxyphenyl                  154 H  H   H  CH.sub. 3                                                                          H      H      isopropyl     methyl     118-120               155 H  H   H  H   H      H      phenyl        n-butyl    108-110               156 H  CH.sub.3                                                                           H  H   H      H      ethyl         phenyl     170-172               157 H  H   H  H   H      H      3-methoxy-    methyl                                                           carbonylphenyl                                 158 H  H   H  H   H      H      methyl        n-decyl    85-87                 159 H  CH.sub.3                                                                           H  H   H      H      phenyl        ethyl      146-148               160 H  H   H  H   H      H      4-phenoxyphenyl                                                                              ethyl                            161 CH.sub.3                                                                          H   CH.sub.3                                                                          H   H      H      propargyl     (3-acetylamino)-                                                               phenyl                           162 H  H   H  H   H      H      phenyl        n-decyl    83-86                 163 H  H   CF.sub.3                                                                          H   H      H      ethyl         phenyl     66-68                 164 H  H   H  H   H      H      2-methoxyethyl                                                                               phenyl     oil                   165 H  H   H  H   H      H      methyl        4(CH.sub.3 SO.sub.2)-phenyl      166 H  H   H  H   H      H      3(CH.sub.3 SO.sub.3)phenyl                                                                   ethyl                            167 H  H   CF.sub.3                                                                          H   H      H      methyl        phenyl     74-76                 168 H  H   H  H   H      H      isopropyl     3-chlorophenyl                                                                            103-105               169 H  H   H  H   H      H      4-tert-butyl- phenyl     161-163                                               cyclohexyl                                     170 H  H   H  H   H      H      phenyl        phenyl     175-176               171 H  H   H  H   H      H      ethyl         3-methylphenyl                                                                            76-78                 172 H  H   H  H   H      H      methyl        4-tert-butyl-                                                                             oil                                                                 cyclohexyl                       173 H  H   CF.sub.3                                                                          H   H      H      3-methylphenyl                                                                               methyl     60-63                 174 H  H   H  H   H      H      methyl        3-chlorophenyl                                                                            155-158               175 H  H   H  H   H      H      phenyl        2-ethyl-n-hexyl                                                                           oil                   176 H  H   H  H   H      H      cyclohexyl    phenyl     189-190               177 H  OCH.sub.3                                                                          H  H   H      H      phenyl        methyl     171-173               178 H  Cl  H  NO.sub.2                                                                           H      H      3-acetylphenyl                                                                               propargyl                        179 H  H   H  H   H      H      2-ethyl-n-hexyl                                                                              methyl     oil                   180 H  H   H  OCH.sub.3                                                                          H      H      phenyl        ethyl      146-148               181 H  H   H  H   H      H      methyl        3-methylphenyl                                                                            137-139               182 H  H   H  H   H      H      4(CH.sub.3).sub.2 NSO.sub.2)phenyl                                                           methyl                           183 H  H   H  H   H      H      3-methylcyclohexyl                                                                           methyl     137-139               184 H  H   H  H   H      H      cyclohexyl    methyl     128-130               185 H  H   H  H   H      H      methyl        propargyl  84-86                 186 H  H   CF.sub.3                                                                          H   H      H      phenyl        isopropyl  75- 77                187 H  H   H  H   H      H      methyl        3-(1'-ethoxycarbo-                                                             nylethoxy)-phenyl                188 H  H   H  CH.sub.3                                                                           H      H      2-chloropropen-                                                                              2-chloropropen-                                                                           103-104                                               (1)-yl-(3)    (1)-yl-(3)                       189 H  H   H  H   ethyl  H      methyl        phenyl                           190 H  CH.sub.3                                                                           H  H   H      H      1-chlorobutyn-                                                                               1-chlorobutyn-                                                                            117-118                                               (2)-yl-(4)    (2)-yl-(4)                       191 H  H   H  H   H      benzyl phenyl        methyl                           192 H  H   H  H   CH.sub.3                                                                              H      methyl        4-fluorophenyl                   193 H  H   H  H   H      H      methyl        methyl     161-163               194 H  H   H  H   H      H      n-butyl       methyl     70-72                 195 H  H   NO.sub.2                                                                          H   H      CH.sub.3                                                                              allyl         4-benzoylphenyl                  196 H  H   H  H   H      H      methyl        methoxyethyl                                                                              76-79                 197 H  H   H  H   H      H      1-naphthyl    ethyl      120-121               198 H  H   H  H   H      H      methyl        ethyl      116-118               199 H  H   H  H   H      C.sub.2 H.sub.5                                                                       methyl        3-methylphenyl                                                                            107-109               200 H  H   H  H   H      H      isopropyl     methyl     110-112               201 H  H   H  H   H      H      3-methyl-5-ethyl-                                                                            methyl     114-116                                               phenyl                                         202 H  H   H  H   C.sub.2 H.sub.5                                                                       H      phenyl        methyl     133-135               203 H  H   H  H   H      H      ethyl         3-methyl-5-ethyl-                                                                         87-89                                                               phenyl                           204 H  H   H  H   H      H      3,3,5-trimethyl-                                                                             methyl     64-67                                                 cyclohexyl                                     205 H  H   H  H   H      H      3,4-(tetra-   methyl     149-151                                               methylenephenyl)                               206 H  H   H  H   H      H      ethyl         norbornyl  86-88                 207 H  H   H  H   CH.sub.3                                                                              H      4-chlorophenyl                                                                               methyl     183-185               208 H  H   H  H   H      H      2-methyl-6-isopro-                                                                           methyl     127-129                                               pylphenyl                                      209 H  H   H  H   H      H      3-methylcyclohexyl                                                                           ethyl      oil                   210 H  H   H  H   H      H      3,5-diethylphenyl                                                                            methyl     113-115               211 H  H   H  H   H      H      2-isopropyl-5-                                                                               methyl     142-144                                               methylphenyl                                   212 H  H   H  H   H      H      ethyl         3,4-(tetra-                                                                               91-93                                                               methylene)-phenyl                213 H  H   H  H   H      H      methyl        2-tert-butyl-4-                                                                           166-168                                                             methylphenyl                     214 H  H   H  H   H      H      tert-amyl     methyl     152-154               215 H  H   H  H   H      H      methyl        hexahydrobenzyl                                                                           85-86                 216 H  H   H  H   H      H      tert-butyl    ethyl       98-100               217 H  H   H  H   H      H      ethyl         isopropyl  117-119               218 H  H   H  H   H      H      cyclohexyl    ethyl      oil                   219 H  H   H  H   H      H      ethyl         2,6-dimethyl-                                                                             oil                                                                 cyclohexyl                       220 H  H   H  H   H      H      4-tert-butylphenyl                                                                           methyl     120-121               221 H  H   H  H   H      H      methyl        2,3,6-trimethyl-                                                                          167-169                                                             phenyl                           222 H  H   H  H   H      H      sec-butyl     methyl     92-94                 223 H  H   H  H   H      H      2,3,5-trimethyl-                                                                             methyl     165-167                                               phenyl                                         224 H  H   H  H   CH.sub.3                                                                              H      methyl        methyl     62-63                 225 H  H   H  H   H      CH.sub.3                                                                              methyl        2,4,6-trimethyl-                                                                          135-137                                                             phenyl                           226 H  H   H  H   H      H      methyl        butyn-1-yl-3                                                                              109-111               227 H  H   H  H   H      H      2,6-dimethoxyphenyl                                                                          methyl                           228 H  H   H  H   H      H      methyl        2,3,5,6-tetra-                                                                            214-216                                                             methylphenyl                     229 H  H   H  H   H      H      CH.sub.3                                                                                      ##STR16## 105-107               230 H  H   H  H   H      H      CH.sub.3                                                                                      ##STR17## oil                   231 H  H   H  H   H      H      CH.sub.3                                                                                      ##STR18##                       232 H  H   H  H   H      H      CH.sub.3                                                                                      ##STR19## 84-86                 233 H  H   H  H   H      H                                                                                      ##STR20##    CH.sub.2CCH                                                                               111-113               234 H  H   H  H   H      H                                                                                      ##STR21##                                                                                    ##STR22## 131-133               235 H  H   H  H   H      H                                                                                      ##STR23##    CH.sub.2 CHCH.sub.2                                                                       95-97                 236 H  H   H  H   H      H                                                                                      ##STR24##                                                                                    ##STR25## oil                   237 H  H   H  H   CH.sub.3                                                                              H                                                                                      ##STR26##                                                                                    ##STR27## 134-136               238 H  H   H  H   C.sub.2 H.sub.5                                                                       H                                                                                      ##STR28##    C.sub.2 H.sub.5                                                                           135-137               239 H  H   H  H   H      H                                                                                      ##STR29##    CH.sub.3  CH.sub.3 CH.sub.3                                                               128-130               240 H  H   H  H   H      H                                                                                      ##STR30##    CH.sub.3  CH.sub.3 CH.sub.3                                                               163-165               241 H  H   H  H   H      H                                                                                      ##STR31##    CH.sub.3   168-170               242 H  H   H  H   H      H                                                                                      ##STR32##    CH.sub.3   167-168               243 H  H   H  H   H      H                                                                                      ##STR33##    CH.sub.3   162-164               244 H  H   H  H   H      H                                                                                      ##STR34##    CH.sub.3   138-140               245 H  H   H  H   H      H                                                                                      ##STR35##    CH.sub.3   131-133               246 H  H   H  H   H      H                                                                                      ##STR36##    CH.sub.3   115-118               247 H  H   H  H   H      H                                                                                      ##STR37##    CH.sub.3   137-139               248 H  H   H  H   H      H                                                                                      ##STR38##    CH.sub.3   118-120               249 H  H   H  H   H      H                                                                                      ##STR39##    CH.sub.3   152-154               250 H  H   H  H   H      H                                                                                      ##STR40##    CH.sub.3   179-181               251 H  H   H  H   H      H                                                                                      ##STR41##    CH.sub.3   130-132               252 H  H   H  H   H      H                                                                                      ##STR42##    CH.sub.3   117-119               253 H  H   H  H   H      H                                                                                      ##STR43##    CH.sub.3   127-129               254 H  H   H  H   H      H                                                                                      ##STR44##    C.sub.2 H.sub.5                                                                           70-72                 255 H  H   H  H   H      H                                                                                      ##STR45##    CH.sub.3   151-152               256 H  H   H  H   H      H                                                                                      ##STR46##    CH.sub.3   145-147               257 H  H   H  H   H      H                                                                                      ##STR47##    CH.sub.3   oil                   258 H  H   H  H   H      H                                                                                      ##STR48##    CH.sub.3   74-76                 259 H  H   H  H   H      H                                                                                      ##STR49##    CH.sub.3   212-214               __________________________________________________________________________

The herbicidal properties of some of the new compounds were examined under controlled conditions and in the open.

GREENHOUSE EXPERIMENTS

Plastic flowerpots having a volume of 300 cm³ were filled with a sandy loam. Seeds were then sown, or vegetatively reproduced species transplanted. The test plants were separated according to species. The active ingredients were suspended or emulsified in water as the vehicle and sprayed onto the surface of the soil by means of atomizing nozzles. After treatment, the vessels were lightly sprinkler-irrigated and then covered with transparent plastic hoods until the plants had taken root. For the postemergence (leaf) treatment, the plants were first grown to a height of from 3 to 10 cm, depending on habit, before being treated. The pots were of course not irrigated, and no hoods were placed on the pots. The plants were placed in either cooler or warmer parts of the greenhouse, depending on their temperature requirements. The experiments were run for from 2 to 4 weeks. During this period the plants were tended and their reaction to the individual treatments was assessed. The application rate of the compounds examined is given in kg/ha of active ingredient. For assessment, the 0 to 100 scale was used, 0 denoting no damage or normal emergence, and 100 denoting no emergence or complete destruction.

EXPERIMENTS IN CLIMATIC CABINETS

Experiments were carried out in climatic cabinets of 1,000 liters volume, with selected agents and sugarbeets and mustard as test plants. The intensity of illumination was 10,000 lux, and the illumination duration 16 hours per day. The relative humidity was adjusted to 80%. Temperature ranges of 12° C. and 22° C. were kept separately so as to be able to ascertain the influence of temperature on the action of the agents.

The test plants were initially grown in the abovementioned pots in the greenhouse until 1 to 2 genuine leaves had developed. The plants were then treated as in the greenhouse experiments and transferred to the climatic cabinets. The observation period lasted 3 weeks. The 0 to 100 scale was again employed for assessment.

EXPERIMENTS IN THE OPEN

Postemergence treatments were carried out on small plots. The compounds were applied, as an emulsion or suspension in water, with the aid of a motor-driven plot spray mounted on a hitch. All the experiments were observed for several weeks and again assessed on the 0 to 100 scale.

RESULTS

The experiments carried out in accordance with the above methods gave the following results. The individual figures are contained in Tables 2 to 14.

1. In addition to a pronounced herbicidal action when applied to leaves, some of the new compounds had a noteworthy herbicidal effect when applied before the test plants had emerged (Tables 2, 11).

2. The herbicidal action on postemergence application was observed in numerous experiments with widely varying plant species from the most different botanical families (Tables 2 to 14). Prior art active ingredients gave in general poorer results than, and in some cases similar results to, the new active ingredients.

3. Numerous agricultural and horticultural crop plants suffered no appreciable damage, if any at all, after treatment with the new compounds (Tables 4, 5, 6, 7, 8, 9, 10, 12, 13); they may therefore be employed as selective herbicidal agents for controlling unwanted plant growth in a number of crop plants. Representatives of the new active ingredients are excellently suited for controlling weeds in soybeans (Table 12). Generally, the new compounds offered clear advantages over the prior art compounds in a wide variety of crops.

                  TABLE 1                                                          ______________________________________                                         List of test plants                                                                          Abbreviation                                                     Botanical name                                                                               in tables    Common name                                         ______________________________________                                         Alopecurus myosuroides                                                                       Alopec. myos.                                                                               slender foxtail                                                                (blackgrass)                                        Amaranthus retroflexus                                                                       Amar. ret.   redroot pigweed                                     Anthemis spp. Anth.        chamomile                                           Arachis hypogaea                                                                             Arach. hyp.  peanuts                                                                        (groundnuts)                                        Beta vulgaris --           sugarbeets                                          Bidens pilosa --           --                                                  Carthamus tinctorius                                                                         Carth. tinct.                                                                               safflower                                           Chenopodium album                                                                            Chen. alb.   common                                                                         lambsquarters                                       Centaurea cyanus                                                                             --           cornflower                                          Cucumis sativus                                                                              Cucum. sat.  cucumber                                            Daucus carota Dauc. car.   carrots                                             Desmodium tortuosum                                                                          Desmod. tort.                                                                               Florida beggarweed                                  Echinochloa crus galli                                                                       Echin. c.g.  barnyardgrass                                       Galinsoga parviflora                                                                         Galin. par.  gallant soldier                                     Glycine max.  Glyc. max.   soybeans                                            Gossypium hirsutum                                                                           Gossyp. hirs.                                                                               cotton                                              Hordeum vulgare                                                                              Hord. vulg.  barley                                              Ipomoea spp.  Ipom. spp.   morningglory                                        Lactuca sativa                                                                               Lac. sat.    lettuce                                             Lamium spp.   --           dead-nettle                                         Molium multiflorum                                                                           --           annual ryegrass                                     Matricaria spp.                                                                              Matr.        chamomile                                           Matricaria inodora                                                                           Matr. inod.  false chemomile                                     Mercurialis annua                                                                            Merc. ann.   annual mercury                                      Petroselinum spp.                                                                            Petr. spp.   parsley                                             Polygonum persicaria                                                                         Poly. per.   ladysthumb                                          Portulaca oleracea                                                                           Port. ol.    common purslane                                     Raphanua raphanistrum                                                                        Raph.        wild radish                                         Sesbania exaltata                                                                            Sesb. exalt. hemp sesbania                                                                  (coffeeweed)                                        Setaria viridis                                                                              Set. vir.    green foxtail                                       Setaria faberii                                                                              --           giant foxtail                                       Sinapis alba  Sinap. alba  white mustard                                       Solanum nigrum                                                                               --           black nightshade                                    Spergula arvensis                                                                            Sperg. arv.  corn spurry                                         Stellaria media                                                                              Stel. med.   chickweed                                           Thlaspi arvense                                                                              Thlas. arven.                                                                               field pennycress                                    Triticum aestivum                                                                            Tritic. aest.                                                                               wheat                                               Xanthium pensylvanicum                                                                       Xanth. pens. common cocklebur                                    Zea mays      --           Indian corn                                         ______________________________________                                    

                  TABLE 2                                                          ______________________________________                                         Herbicidal action of some new compounds;                                       preemergence treatment in the greenhouse                                       Active                                                                         ingredient          Test plants and % damage                                   no.        kg/ha    Sesbania exaltata                                                                            Sinapis alba                                 ______________________________________                                         23         3.0      --             80                                          13         3.0      --            100                                           8         3.0      100           --                                           46         3.0       90           --                                            7         2.0      --            100                                          ______________________________________                                          0 = no damage                                                                  100 = no emergence or plants destroyed                                   

                                      TABLE 3                                      __________________________________________________________________________     Herbicidal action of some new compounds; postemergence treatment in the        open                                                                           Active    Test plants and % damage                                             ingredient                                                                               Alopec.                                                                            Anth.                                                                              Chen.                                                                              Echin.                                                                             Galin.                                                                             Poly.                                                                             Raph.                                                                              Sperg.                                                                             Thlas.                                no.   kg/ha                                                                              myos                                                                               Matr.                                                                              alb.                                                                               c. g.                                                                              par.                                                                               per.                                                                              Sina.                                                                              arv.                                                                               arven.                                __________________________________________________________________________     2     0.5 35  45  100 50   98  95                                                                                98 100 62                                          1.0 65  78  100 75  100 100                                                                                98 100 75                                          2.0 90  88  100 90  100 100                                                                               100 100 80                                    7     0.5 30   8  100 45   92  90                                                                                80 100 93                                          1.0 50  10  100 65   98 100                                                                                95 100 100                                         2.0 70  20  100 72   98 100                                                                                98 100 100                                   181   0.5 50  52  100 58  100  85                                                                               100 100 80                                          1.0 70  78  100 80  100 100                                                                               100 100 95                                          2.0 85  92  100 95  100 100                                                                               100 100 100                                   __________________________________________________________________________      0 = no damage                                                                  100 = plants destroyed                                                   

                                      TABLE 4                                      __________________________________________________________________________     Selective herbicidal action of various compounds;                              postemergence treatment in the greenhouse                                                              Test plants and % damage                               Active                      Cu-                          Sin-                                                                              Stell.             ingredient              Arach.                                                                             cum.                                                                              Dauc.                                                                              Glyc.                                                                              Petr.                                                                             Amar.                                                                              Chen.                                                                              Merc.                                                                              Sesb.                                                                             ap.                                                                               med-               no.                 kg/ha                                                                              hyp.                                                                               sat.                                                                              car.                                                                               max spp.                                                                              ret.                                                                               alb.                                                                               ann.                                                                               exalt                                                                             alba                                                                              ia                 __________________________________________________________________________     35                  2.0 0   10  0   0   0 100 95   90 75  95                                                                               95                  ##STR50##          2.0 0   40 20  20  40  98 95  100 85 100                                                                               70                 prior art                                                                      __________________________________________________________________________      0 = no damage                                                                  100 = plants destroyed                                                   

                                      TABLE 5                                      __________________________________________________________________________     Selective herbicidal action of various compounds;                              postemergence treatment in the greenhouse                                      Active             Test plants and % damage                                    ingredient         Arach.                                                                             Glyc.                                                                              Gossyp.                                                                             Desmod.                                                                              Sesb.                                                                              Xanth.                               no.            kg/ha                                                                              hyp.                                                                               max hirs.                                                                               tort. exalt.                                                                             penns.                               __________________________________________________________________________     2              1.0 0   15   0   78     90 20                                                  2.0 0   15  10   78     90 80                                    ##STR51##     1.0 2.0                                                                            0 0 30 30                                                                              10 20                                                                                5 70 100 100                                                                            10 30                                prior art                                                                       ##STR52##     1.0 2.0                                                                            0 0 0 0 70 70                                                                                0  0 100 100                                                                            90 90                                prior art                                                                      __________________________________________________________________________      0 = no damage                                                                  100 = plants destroyed                                                   

                                      TABLE 6                                      __________________________________________________________________________     Selective herbicidal action of various compounds;                              postemergence treatment in the greenhouse                                                               Test plants and % damage                              Active                   A- Cu-    Gos-  A- I-              Si-                ingredient               rach.                                                                             cum.                                                                              Dauc.                                                                              syp.                                                                              Petr.                                                                             mar.                                                                              pom.                                                                              Merc.                                                                              Port.                                                                             Sesb.                                                                             Set.                                                                              nap.               no.                  kg/ha                                                                              hyp                                                                               sat.                                                                              car.                                                                               hirs.                                                                             spp.                                                                              ret.                                                                              spp.                                                                              ann.                                                                               ol.                                                                               exalt                                                                             vir.                                                                              alba               __________________________________________________________________________      7                   0.5 --  0  0  20  0  65                                                                                95                                                                               70   95                                                                                95                                                                                70                                                                                60                                     1.0  0 -- 10  20  0  75                                                                               100                                                                               70  100                                                                                95                                                                               100                                                                               100                 2                   0.5 -- 20  0   0  0  70                                                                                80                                                                                0  100                                                                                35                                                                               100                                                                                95                                     1.0 10 20  0  10  0 100                                                                                80                                                                                0  100                                                                               100                                                                               100                                                                               100                181                  0.5 -- 20  0  20  0  55                                                                               100                                                                               95   90                                                                                55                                                                                90                                                                               100                                     1.0 10 20  0  40  0  65                                                                               100                                                                               95   90                                                                               100                                                                               100                                                                               100                 ##STR53##           0.5 1.0                                                                            -- 40 50                                                                             35 45                                                                              25 45                                                                             10 85                                                                              0  40 52                                                                            30 30                                                                              100 100                                                                            90 100                                                                            90 95                                                                             92 98             __________________________________________________________________________      0 = no damage                                                                  100 = plants destroyed                                                   

                                      TABLE 7                                      __________________________________________________________________________     Herbicidal action and tolerance by crop plants of various compounds;           postemergence treatment in the greenhouse                                      Active                   Test plants and % damage                              ingredient               Arach.                                                                             Glyc.                                                                              Hord.                                                                              Lact.                                                                             Tritic.                                                                            Amar.                                                                              Chen.                                                                              Sesb.                                                                             Sinap.                                                                             Stell.              no.                  kg/ha                                                                              hyp.                                                                               max vulg.                                                                              sat.                                                                              aest.                                                                              ret.                                                                               alb.                                                                               exalt                                                                             alba                                                                               media               __________________________________________________________________________     184                  2.0 0   0   0    0 0   80  80  100                                                                                90 80                   ##STR54##           2.0 0   10  25  30 60  30  95   90                                                                               100 90                  prior art                                                                       ##STR55##           2.0 0   0   0   90 0   20  95   85                                                                               100 95                  prior art                                                                      __________________________________________________________________________      0 = no damage                                                                  100 = plants destroyed                                                   

                                      TABLE 8                                      __________________________________________________________________________     Selective herbicidal action of various compounds;                              postemergence treatment in the greenhouse                                      Active                   Test plants and % damage                              ingredient               Arach.                                                                             Glyc.                                                                             Amar.                                                                              Merc.                                                                              Port.                                                                             Sesb.                                                                              Set.                                                                              Sinap.                                                                             Stell.                   no.                  kg/ha                                                                              hyp.                                                                               max                                                                               ret.                                                                               ann.                                                                               ol.                                                                               exalt.                                                                             vir.                                                                              alba                                                                               media                    __________________________________________________________________________     13                   0.5 --  10  45 95  100                                                                               100  85                                                                               100 90                                            1.0 10  10  50 95  100                                                                               100  85                                                                               100 90                       8                    0.5 --  0   98 40  100                                                                                70 100                                                                                50 80                                            1.0 0   0  100 70  100                                                                                70 100                                                                                50 80                        ##STR56##           0.5 1.0                                                                            -- 0                                                                               0 0                                                                                0  60 60                                                                              100 100                                                                            90 90                                                                              90 90                                                                             90 100                                                                            90 90                    prior art                                                                       ##STR57##           0.5 1.0                                                                            -- 0                                                                               0 0                                                                                0  10                                                                             40 80                                                                              100 --                                                                             85 85                                                                              10 40                                                                            100 100                                                                            95 95                    prior art                                                                      __________________________________________________________________________      0 = no damage                                                                  100 = plants destroyed                                                   

                  TABLE 9                                                          ______________________________________                                         Tolerance by sugarbeets and herbicidal                                         action of various compounds;                                                   postemergence treatment in climatic cabinet                                                          Test plants and                                                                % damage                                                                       Temperature                                                                    range °C.                                         Active                      Sugar-  Sinapis                                    ingredient                  beets   alba                                       no.                 kg/ha   11    22  11  22                                   ______________________________________                                         2                   0.5      0     0  70   92                                                      1.0     12     2  75   92                                                      2.0     10     2  85  100                                   ##STR58##          0.5 1.0 2.0                                                                             0 0 7                                                                               10 10 10                                                                           88 90 90                                                                            95 100 100                          prior art                                                                      ______________________________________                                          0 = no damage                                                                  100 = plants destroyed                                                   

                                      TABLE 10                                     __________________________________________________________________________     Selective herbicidal action of new diurethanes; postemergence treatment        in the greenhouse                                                               ##STR59##                                                                     Active                Test plants and % damage                                 ingredient                                                                           Substituent     Arach.                                                                             Carth.                                                                             Dauc.                                                                              Hord.                                                                              Tritic.                                                                            Zea Desmod.                                                                             Sesb.                                                                              Sinap.                                                                             Stell.              no.   R           kg/ha                                                                              hyp.                                                                               tinct.                                                                             car.                                                                               vulg.                                                                              aest.                                                                              mays                                                                               tort.                                                                               exalt.                                                                             alba                                                                               med.                __________________________________________________________________________            ##STR60##  1.0 2.0                                                                            10  20                                                                             0 0 0 0 0 0 0 0 10  15                                                                              100 100                                                                            90 95                                                                               99 99                                                                              30  70             90                1.0  0  0   0   0   0    0  100  95   75 100                                   2.0  0  0   0   0   0    0  100  95   95 100                 82                1.0  0  0   0   0   0    0  100  95   99 100                                   2.0  0  0   0   0   0    0  100  95  100 100                 105               1.0  0  0   0   --  0    0  100  45  100 --                                    2.0  0  0   0   --  0    0  100  50  100 --                  172               1.0  0  0   --  0   --   0   30  50   60 100                                   2.0 20  0   --  0   0    0  100  60  100 --                  __________________________________________________________________________      0 = no damage                                                                  100 = plants destroyed                                                   

                                      TABLE 11                                     __________________________________________________________________________     Preemergence action of new diurethanes; greenhouse application                 Active                           Test plants and % damage                      ingredient                       Amar.                                                                              Bidens                                                                             Matr.                                                                              Sinap.                                                                             Solanum                                                                             Stell.                   no.   Compounds              kg/ha                                                                              ret.                                                                               pilosa                                                                             inod.                                                                              alba                                                                               nigrum                                                                              med.                     __________________________________________________________________________     85                           1.0 90  100 100 98  65   98                                                    2.0 95  100 100 98  90   98                              ##STR61##             1.0 2.0                                                                             0  0                                                                               10  40 40 50                                                                              10 15                                                                               50 70                           ##STR62##             1.0 2.0                                                                            60 80                                                                               95 100                                                                            100 100                                                                            95 95                                                                              55 70                                                                               60 70                    __________________________________________________________________________      0 = no damage                                                                  100 = plants destroyed                                                   

                                      TABLE 12                                     __________________________________________________________________________     Tolerance by various soybean species; postemergence application in the         greenhouse                                                                     Active                % damage in soybean species and other test plants        ingredient            SRF                         Setaria.sup.x                                                                        Sesb..sup.x                                                                         Stell.            no.   Compound    kg/ha                                                                              450                                                                               Dare                                                                              Lee 68                                                                             Bragg                                                                              Prata                                                                              Prenola                                                                             Planato                                                                             faberii                                                                             exalt.                                                                              media              __________________________________________________________________________     8                 0.5 0  0  0   0   0   0    0    10   60    40                8     + linseed oil emulsi-                                                                      0.5 0  10 0   15  0   0    0    100  95   100                      fied in water in                                                               amount of 4 vol %                                                              of spray liquor                                                                 ##STR63##  0.5 0  0  0   0   0   0    0    0    40   100                       ##STR64##  0.5 0  10 0   0   10  10   10   0    80   100                + linseed oil emulsified in water in amount of 4 vol % of spray                __________________________________________________________________________     liquor.                                                                         0 = no damage                                                                  100 = plants destroyed                                                         .sup.x = larger plants than in Table 8                                   

                                      TABLE 13                                     __________________________________________________________________________     Selective herbicidal action in beets; postemergence treatment                  in the greenhouse                                                              Active          Test plants and % damage                                       ingredient      Beta                                                                              Hord.                                                                              Chen.                                                                              Lamium                                                                              Merc.                                                                              Sinapis                                    no.   Compound                                                                             kg/ha                                                                              vulg.                                                                             vulg.                                                                              alb.                                                                               spp. annua                                                                              alba                                       __________________________________________________________________________     101         1.0 0  0   80  100   80  98                                                    2.0 0  0   --  100  100 100                                        __________________________________________________________________________      0 = no damage                                                                  100 = plants destroyed                                                   

                  TABLE 14                                                         ______________________________________                                         Herbicidal action of new compounds; preemergence (PRE) and                     postemergence (POST) treatment in greenhouse                                               Test plants and % damage                                           Active                             Lolium Sin-                                 ingredient        Centaurea Ipomoea                                                                               multi- apis                                 no.     kg/ha     cyanus    spp.   florum alba                                 ______________________________________                                         204     3.0 PRE   --        0      0      100                                          3.0 POST  100       0      95     --                                   209     3.0 PRE   --        0      10     80                                           3.0 POST  100       100    40     --                                   205     3.0 PRE   --        0      0       0                                           3.0 POST  80        80     40      0                                   212     3.0 PRE   --        0      0       0                                           3.0 POST  80        20     40     --                                   199     3.0 PRE   --        0      0      40                                           3.0 POST  80        60     40     --                                   202     3.0 PRE   --        40     80     80                                           3.0 POST  80        80     80     --                                   201     3.0 PRE   --        0      20      0                                           3.0 POST  80        80     80     --                                   216     3.0 PRE   --        80     50     40                                           3.0 POST  100       100    90     --                                   ______________________________________                                          0 = no damage                                                                  100 = plants destroyed                                                   

The new active ingredients may be incorporated into the soil, or applied to the surface of the soil or to emerged plants. It is also possible to eliminate unwanted plants by post-directed or lay-by applications. In this case, the spray is directed in such a manner that the leaves of sensitive crop plants are not--or only slightly--touched, and the soil and smaller weeds are fully contacted.

In view of the application possibilities, the herbicides according to the invention or compositions containing them may not only be used in the crops listed in the tables but also in a much wider range of crops for removing unwanted plants. The amount of active ingredient applied may vary from 0.1 to 15 kg/ha and more, depending on the weeds to be controlled. The following crops may be mentioned by way of example:

    ______________________________________                                         Botanical name       Common name                                               ______________________________________                                         Allium cepa          onions                                                    Ananas comosus       pineapple                                                 Asparagus officinalis                                                                               asparagus                                                 Avena sativa         oats                                                      Beta vulgaris spp. rapa                                                                             fodder beets                                              Beta vulgaris spp. esculenta                                                                        table beets, red beets                                    Brassica napus var. napus                                                                           rape                                                      Brassica napus var. napobrassica                                               Brassica napus var. rapa                                                                            turnips                                                   Brassica rapa var. silvestis                                                   Camellia sinensis    tea plants                                                Carthamus tinctorius safflower                                                 Citrus limon         lemon                                                     Citrus maxima        grapefruit                                                Citrus reticulata                                                              Citrus sinensis      orange trees                                              Coffea arabica (Coffea canephora,                                                                   coffee plants                                             Coffea liberica)                                                               Cucumis melo         melons                                                    Cynodon dactylon     Bermudagrass in                                                                turf and lawns                                            Elaeis guineensis    oil palms                                                 Fragaria vesca       strawberries                                              Gossypium arboreum                                                             Gossypium herbaceum  cotton                                                    Gossypium vitifolium                                                           Helianthus annuus    sunflowers                                                Helianthus tuberosus                                                           Hevea brasiliensis   rubber plants                                             Humulus lupulus      hops                                                      Ipomoea batatas      sweet potato                                              Lens culinaris       lentils                                                   Linium usitatissimum flax                                                      Lycopersicon lycopersicum                                                                           tomato                                                    Malus spp.           apple trees                                               Manihot esculenta    cassava                                                   Medicago sativa      alfalfa (lucerne)                                         Mentha piperita      peppermint                                                Musa spp.            banana plants                                             Nicotiana tabacum    tobacco                                                   ( N. rustica )                                                                 Olea europaea        olive trees                                               Oryza sativa         rice                                                      Panicum miliaceum                                                              Phaseolus lunatus    limebeans                                                 Phaseolus mungo      mungbeans                                                 Phaseolus vulgaris   snapbeans, green beans,                                                        dry beans                                                 Pennisetum glaucum                                                             Picea abies                                                                    Pinus                pine trees                                                Pisum sativum spp. sativum                                                                          English peas                                              Prunus avium         cherry trees                                              Pranus domestica     plum trees                                                Prunus persica       peach trees                                               Pyrus communis       pear trees                                                Ribes sylvestre      redcurrants                                               Ribes uva-crispa                                                               Ricinus communis                                                               Saccharum officinarum                                                                               sugar cane                                                Secale cereale       rye                                                       Solanum tuberosum    Irish potatoes                                            Sorghum bicolor (s. vulgare)                                                                        grain sorghum                                             Sorghum dochna                                                                 Spinacia oleracea    spinach                                                   Theobroma cacao      cacao plants                                              Trifolium pratense   red clover                                                Vaccinium corymbosum blueberry                                                 Vaccinium vitis-idaea                                                                               cranberry                                                 Vicia faba           tick beans                                                Vigna sinensis (V. unguiculata)                                                                     cow peas                                                  Vitis vinifera       grapes                                                    Zea mays             Indian corn, sweet                                                             corn, maize                                               ______________________________________                                    

To broaden the spectrum of action of the new individual compounds, to achieve synergistic effects or to improve persistence in the soil, the compounds according to the invention may be mixed with each other, and numerous other herbicidal and growth-regulating compounds may be used as mixture and combination components. Depending on area of use and objective, the following substances or similar derivatives may be used in mixtures:

    ______________________________________                                          ##STR65##                                                                     R                  R.sup.1                                                     ______________________________________                                          ##STR66##         NH.sub.2                                                     ##STR67##         NHCH.sub.3                                                   ##STR68##         NHCH.sub.3                                                   ##STR69##         NH.sub.2                                                    ______________________________________                                          ##STR70##                                                                     R           R.sup.1      R.sup.2                                               ______________________________________                                                      ##STR71##   H and salts                                           H                                                                                           ##STR72##   Cl and salts                                          H                                                                                           ##STR73##   F and salts                                           H                                                                                           ##STR74##   CH.sub.3 and salts                                    CH.sub.2 OCH.sub.3                                                                          ##STR75##   H                                                     ______________________________________                                          ##STR76##                                                                      ##STR77##                                                                     R.sup.1     R.sup.2      R.sup.3                                               ______________________________________                                         CF.sub.3    n . C.sub.3 H.sub.7                                                                         n . C.sub.3 H.sub.7                                   CF.sub.3    n . C.sub.3 H.sub.7                                                                         CH.sub.2CH.sub.2 Cl                                   SO.sub.2 NH.sub.2                                                                          n . C.sub.3 H.sub.7                                                                         n . C.sub.3 H.sub.7                                   ______________________________________                                          ##STR78##                                                                     R.sup.1       R.sup.2  R.sup.3                                                 ______________________________________                                         CH.sub.3      H                                                                                        ##STR79##                                               ##STR80##    H        i-C.sub.3 H.sub.7                                        ##STR81##    H                                                                                        ##STR82##                                               ##STR83##    H                                                                                        ##STR84##                                               ##STR85##    H        i-C.sub.3 H.sub.7                                        ##STR86##    H        CH.sub.2CCCH.sub.2 Cl                                    ##STR87##    H                                                                                        ##STR88##                                               ##STR89##    H        CH.sub.3                                                 ##STR90##    H        CH.sub.3                                                ______________________________________                                          ##STR91##                                                                      ##STR92##                                                                     R.sup.1       R.sup.2      R.sup.3                                             ______________________________________                                          ##STR93##    H            C.sub.2 H.sub.5                                      ##STR94##    CH.sub.3     CH.sub.3                                            ______________________________________                                          ##STR95##                                                                     R.sup.1        R.sup.2      R.sup.3                                            ______________________________________                                          ##STR96##     H            CH.sub.3                                            ##STR97##     H            C.sub.2 H.sub.5                                     ##STR98##     H            CH.sub.3                                            ##STR99##     H            C.sub.2 H.sub.5                                    ______________________________________                                          ##STR100##                                                                    R.sup.1    R.sup.2       R.sup.3                                               ______________________________________                                         i-C.sub.3 H.sub.7                                                                         i-C.sub.3 H.sub.7                                                                            CH.sub.2CClCHCl                                       n . C.sub.3 H.sub.7                                                                       n . C.sub. 3 H.sub.7                                                                         C.sub.2 H.sub.5                                       n . C.sub.3 H.sub.7                                                                       n . C.sub.3 H.sub.7                                                                          n . C.sub.3 H.sub.7                                   sec . C.sub.4 H.sub.9                                                                     sec . C.sub.4 H.sub.9                                                                        C.sub.2 H.sub.5                                       C.sub.2 H.sub.5                                                                           C.sub.2 H.sub.5                                                                               ##STR101##                                            ##STR102##                                                                               C.sub.2 H.sub.5                                                                              C.sub.2 H.sub.5                                        ##STR103##                                                                               C.sub.2 H.sub.5                                                                              C.sub.2 H.sub.5                                       ______________________________________                                          ##STR104##                                                                     ##STR105##                                                                    ______________________________________                                         C.sub.2 H.sub.5                                                                n . C.sub.3 H.sub.7                                                             ##STR106##                                                                    ______________________________________                                          ##STR107##                                                                    R.sup.1           X      Y       R.sup.2                                       ______________________________________                                         CH.sub.3          Cl     Cl      Na                                            Cl                Cl     Cl      Na                                            C.sub.2 H.sub.5   Cl     Cl      Na                                             ##STR108##       Cl     H       CH.sub.3                                       ##STR109##       H      H       H and salts                                    ##STR110##       H      Cl      NH.sub.4                                       ##STR111##       H      CH.sub.3                                                                               C.sub.2 H.sub.5                                ##STR112##       H      CH.sub.3                                                                               CH.sub.3                                       ##STR113##       H      CH.sub.3                                                                               i-C.sub.3 H.sub.7                              ##STR114##       H      CH.sub. 3                                                                               ##STR115##                                    ##STR116##       H      CH.sub.3                                                                               CH.sub.3                                      ______________________________________                                          ##STR117##                                                                     ##STR118##                                                                     ##STR119##                                                                     ##STR120##                                                                    R.sup.1   X           R.sup.2                                                  ______________________________________                                         i-C.sub.3 H.sub.7                                                                        Cl          C.sub. 2 H.sub.5                                         i-C.sub.3 H.sub.7                                                                        Cl                                                                                          ##STR121##                                              i-C.sub.3 H.sub.7                                                                        Cl          i-C.sub.3 H.sub.7                                        C.sub.2 H.sub.5                                                                          Cl          C.sub.2 H.sub.5                                          C.sub.2 H.sub.5                                                                          Cl          C(CH.sub.3).sub.2 CN                                     C.sub.2 H.sub.5                                                                          Cl                                                                                          ##STR122##                                              C.sub.2 H.sub.5                                                                          Cl                                                                                          ##STR123##                                               ##STR124##                                                                              Cl          C(CH.sub.3).sub.2CN                                      i-C.sub.3 H.sub.7                                                                        OCH.sub.3   i-C.sub.3 H.sub.7                                        i-C.sub.3 H.sub.7                                                                        SCH.sub.3   C.sub.2 H.sub.5                                          C.sub.2 H.sub.5                                                                          SCH.sub.3   C.sub.2 H.sub.5                                          C.sub.2 H.sub.5                                                                          SCH.sub.3   tert . C.sub.4 H.sub.9                                   ______________________________________                                          ##STR125##                                                                    X            Y            R                                                    ______________________________________                                         CF.sub.3     H            CH.sub.3                                             H            F            CH.sub.3                                             ______________________________________                                          ##STR126##                                                                    R.sup.1     R.sup.2        R.sup.3                                             ______________________________________                                          ##STR127##                                                                                 ##STR128##    CH.sub.2 Cl                                          ##STR129##                                                                                 ##STR130##    CH.sub.2 Cl                                          ##STR131## CH.sub.2CH.sub.2OCH.sub.3                                                                     CH.sub.2 Cl                                          ##STR132## CH.sub.2OCH.sub.3                                                                             CH.sub.2 Cl                                          ##STR133##                                                                                 ##STR134##    CH.sub.2 Cl                                          ##STR135## CH.sub.2OC.sub.4 H.sub. 9 n                                                                   CH.sub.2 Cl                                          ##STR136##                                                                                 ##STR137##    CH.sub.2 Cl                                          ##STR138## H                                                                                              ##STR139##                                          ##STR140## H                                                                                              ##STR141##                                          ##STR142## H              C.sub.2 H.sub.5                                      ##STR143## H              C(CH.sub.3).sub.2C.sub.3 H.sub.7                     ##STR144## H              CH.sub.3                                             ##STR145## H              CH.sub.3                                             ##STR146## H                                                                                              ##STR147##                                         ______________________________________                                          ##STR148##                                                                     ##STR149##                                                                    X           X.sub.1       R                                                    ______________________________________                                         Br          Br            H and salts                                          J           J             H and salts                                          Br          Br                                                                                            ##STR150##                                          ______________________________________                                          ##STR151##                                                                    R         R.sup.1     R.sup.2    R.sup.3                                       ______________________________________                                         Cl        Cl          Cl         H                                             F         Cl          Cl         H                                             Cl        Cl          H          H                                             Cl        CF.sub.3    H          COOH                                          Cl        Cl          H          COOCH.sub.3                                   NO.sub.2  CF.sub.3    H          H                                             H         CF.sub.3    Cl         H                                             H         CF.sub.3    Cl         OC.sub.2 H.sub.5                              Cl        Cl          H          OCH.sub.3                                     ______________________________________                                          ##STR152##                                                                    R.sup.1         R.sup.2                                                                               R.sup.3 R.sup.4                                         ______________________________________                                          ##STR153##     H      CH.sub.3                                                                               CH.sub.3                                         ##STR154##     H      CH.sub.3                                                                               CH.sub.3                                         ##STR155##     H      CH.sub.3                                                                               CH.sub.3                                         ##STR156##     H      CH.sub.3                                                                               CH.sub.3                                         ##STR157##     H      CH.sub.3                                                                               CH.sub.3                                         ##STR158##     H      CH.sub.3                                                                                ##STR159##                                      ##STR160##                                                                                    H      CH.sub.3                                                                               CH.sub.3                                         ##STR161##     H      CH.sub.3                                                                               OCH.sub.3                                        ##STR162##     H      CH.sub.3                                                                               CH.sub.3                                         ##STR163##     H      CH.sub.3                                                                               OCH.sub.3                                        ##STR164##     H      CH.sub.3                                                                               CH.sub.3                                         ##STR165##     H      CH.sub.3                                                                               CH.sub.3                                         ##STR166##     H      CH.sub.3                                                                               OCH.sub.3                                        ##STR167##     H      CH.sub.3                                                                               CH.sub.3                                         ##STR168##     H      CH.sub.3                                                                               OCH.sub.3                                        ##STR169##     H      CH.sub.3                                                                               OCH.sub.3                                        ##STR170##     H      CH.sub.3                                                                               CH.sub.3                                         ##STR171##     CH.sub.3                                                                              H       CH.sub.3                                        ______________________________________                                          ##STR172##                                                                     ##STR173##                                                                     ##STR174##                                                                     ##STR175##                                                                    R       R.sup.1        R.sup.2                                                 ______________________________________                                         tert . C.sub.4 H.sub.9                                                                 NH.sub.2       SCH.sub.3                                               tert . C.sub.4 H.sub.9                                                                  ##STR176##    SCH.sub.3                                                ##STR177##                                                                            NH.sub. 2      CH.sub.3                                                ______________________________________                                          ##STR178##                                                                    R.sup.1 R.sup.2   R.sup.3                                                      ______________________________________                                         CH.sub.3                                                                               Br        sec . C.sub.4 H.sub.9                                        CH.sub.3                                                                               Cl        tert . C.sub.4 H.sub.9                                       CH.sub.3                                                                               Cl                                                                                        ##STR179##                                                  CH.sub.2CH.sub.2CH.sub.2                                                                      ##STR180##                                                      ______________________________________                                          ##STR181##                                                                    R.sup.1                                                                             R.sup.2                                                                   ______________________________________                                         CH.sub.3                                                                            CH.sub.3                                                                  CH.sub.3                                                                             ##STR182##                                                               ______________________________________                                          ##STR183##                                                                     ##STR184##                                                                    R.sup.1    R.sup.2      R.sup.3                                                ______________________________________                                          ##STR185##                                                                               sec . C.sub.4 H.sub.9                                                                       H                                                       ##STR186##                                                                               tert . C.sub.4 H.sub.9                                                                      H                                                       ##STR187##                                                                               tert . C.sub.4 H.sub.9                                                                      CH.sub.3                                               H          CH.sub.3     H salts and esters                                     H          sec . C.sub.4 H.sub.9                                                                       H salts and esters                                     H          tert . C.sub.4 H.sub.9                                                                      H salts and esters                                     H          tert . C.sub.4 H.sub.9                                                                      CH.sub.3 salts and esters                              ______________________________________                                          ##STR188##                                                                    R.sup.1                                                                        ______________________________________                                          ##STR189##                                                                     ##STR190##                                                                     ##STR191##                                                                    ______________________________________                                          ##STR192##                                                                     ##STR193##                                                                    R.sup.1      X                                                                 ______________________________________                                         H            CH.sub.3 OSO.sub.3                                                Br           CH.sub.3 OSO.sub.3                                                CH.sub.3     CH.sub.3 OSO.sub.3                                                CH.sub.3     CF.sub.3 SO.sub.3                                                 ______________________________________                                          ##STR194##                                                                     ##STR195##                                                                     ##STR196##                                                                     ##STR197##                                                                     ##STR198##                                                                     ##STR199##                                                                     ##STR200##                                                                     ##STR201##                                                                     ##STR202##                                                                     ##STR203##                                                                    R.sup.1  R.sup.2    R.sup.3     R.sup.4                                        ______________________________________                                         H        Cl         NH.sub.2    Cl                                             H        I          I           I                                              Cl       H          Cl          OCH.sub.3                                      Cl       Cl         H           Cl                                             Cl       Cl         Cl          OCH.sub.3                                      ______________________________________                                          ##STR204##                                                                    R.sup.1     R.sup.2  R.sup.3                                                   ______________________________________                                          ##STR205## H        H       salts, esters, amides                              ##STR206## CH.sub.3 H       salts, esters, amides                              ##STR207## H        H       salts, esters, amides                              ##STR208## CH.sub.3 H       salts, esters, amides                              ##STR209## H        H       salts, esters, amides                              ##STR210## CH.sub.3 H       salts, esters, amides                             ______________________________________                                          ##STR211##                                                                     ##STR212##                                                                     ##STR213##                                                                     ##STR214##                                                                     ##STR215##                                                                     ##STR216##                                                                     ##STR217##                                                                     ##STR218##                                                                     ##STR219##                                                                     ##STR220##                                                                     ##STR221##                                                                    R.sup.1                                                                        OH                                                                             CH.sub.3                                                                        ##STR222##                                                                     ##STR223##                                                                     ##STR224##                                                                     ##STR225##                                                                     ##STR226##                                                                     ##STR227##                                                                    ______________________________________                                    

It is also possible to apply the compounds of the invention either alone or in combination with other herbicides, in admixture with other crop protection agents, for example agents for combatting pests or phytopathogenic fungi or bacteria. Of further interest is the fact that the compounds of the invention may be mixed with solutions of mineral fertilizers used to eliminate trace element or nutritional deficiencies.

Spreader-stickers and non-phytotoxic oils may be added to the compounds of the invention to ensure that they take effect.

The new compounds have a good fungicidal action for example on phytopathogenic fungi, especially rusts, for instance in cereals and beans. The following fungi for example may be controlled: Puccinia coronata in oats, Puccinia hordei in barley, Puccinia striiformis and Puccinia recondita in wheat, and Uromyces fabae and Uromyces appendiculatus in beans.

Application rates are from 0.2 to 1 kg of active ingredient per hectare.

EXAMPLE 2

Leaves of barley plants of the Asse variety and wheat plants of the Caribo variety, grown in pots, are artificially infected with spores of Puccinia hordei or Puccinia recondita, and the plants are placed for 24 hours in a steam-saturated chamber at 20° to 25° C. The plants are then sprayed with aqueous spray liquors containing (dissolved or emulsified in the water) a mixture of 80% of the active ingredient to be examined and 20of lignin sulfate, and placed in the greenhouse at from 20° to 22° C. and a relative humidity of from 75 to 80%. The extent to which the rust fungus has spread is assessed after 10 days.

    ______________________________________                                                        Attack after spraying with liquor                                              containing 0.05% active ingredient                              Active           Puccinia                                                      ingredient       hordei     Puccinia recondita                                 ______________________________________                                          7               0          0                                                   2               0          0                                                   8               0          0                                                   ##STR228##      1          2                                                  prior art (German                                                              Laid-Open Application                                                          DOS 1,567,211)                                                                 Control (untreated)                                                                             5                                                             ______________________________________                                          0 = no attack, graduated down to 5 = 100% attack                         

EXAMPLE 3

As described in Example 2, leaves of oat plants of the Flaingskrone variety grown in pots are artificially infected with spores of Puccinia coronata, and sprayed with aqueous suspensions of the active ingredients given in the Table.

    ______________________________________                                                          Attack after spraying with                                    Active           liquor containing 0.05%                                       ingredient       active ingredient                                             ______________________________________                                          2               0                                                              8               0                                                              ##STR229##      1-2                                                           prior art (German                                                              Laid-Open Application                                                          DOS 1,567,211)                                                                 Control (untreated)                                                                             5                                                             ______________________________________                                    

EXAMPLE 4

As described in Example 2, leaves of bean plants of the Mombacher Speck variety grown in pots are artificially infected with spores of Uromyces fabae, and treated with aqueous suspensions of the active ingredients given in the Table.

    ______________________________________                                                          Attack after spraying with                                    Active           liquor containing 0.05%                                       ingredient       active ingredient                                             ______________________________________                                          7               1-2                                                            8               0                                                              ##STR230##      2                                                             prior art (German                                                              Laid-Open Application                                                          DOS 1,567,211)                                                                 Control (untreated)                                                                             5                                                             ______________________________________                                    

Application may be effected for instance in the form of directly sprayable solutions, powders, suspensions, dispersions, emulsions, oil dispersions, pastes, dusts, broadcasting agents, or granules by spraying, atomizing, dusting, broadcasting or watering. The forms of application depend entirely on the purpose for which the agents are being used; in any case they should ensure a fine distribution of the active ingredient.

For the preparation of solutions, emulsions, pastes and oil dispersions to be sprayed direct, mineral oil fractions of medium to high boiling point, such as kerosene or diesel oil, further coal-tar oils, etc. and oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons such as benzene, toluene, xylene, paraffin, tetrahydronaphthalene, alkylated naphthalenes and their derivatives such as methanol, ethanol, propanol, butanol, chloroform, carbon tetrachloride, cyclohexanol, cyclohexanone, chlorobenzene, isophorone, etc., and strongly polar solvents such as dimethylformamide, dimethyl sulfoxide, N-methypyrrolidone, water, etc. are suitable.

Aqueous formulations may be prepared from emulsion concentrates, pastes, oil dispersions or wettable powders by adding water. To prepare emulsions, pastes and oil dispersions the ingredients as such or dissolved in an oil or solvent may be homogenized in water by means of wetting or dispersing agents, adherents or emulsifiers. Concentrates which are suitable for dilution with water may be prepared from active ingredient, wetting agent, adherent, emulsifying or dispersing agent and possibly solvent or oil.

Examples of surfactants are: alkali metal, alkaline earth metal and ammonium salts of ligninsulfonic acid, naphthalenesulfonic acids, phenolsulfonic acids, alkylaryl sulfonates, alkyl sulfates, and alkyl sulfonates, alkali metal and alkaline earth metal salts of dibutylnaphthenesulfonic acid, lauryl ether sulfate, fatty alcohol sulfates, alkali metal and alkaline earth metal salts of fatty acids, salts of sulfated hexadecanols, heptadecanols,and octadecanols, salts of sulfated fatty alcohol glycol ether, condensation products or sulfonated naphthalene and naphthalene derivatives with formaldehyde, condensation products of naphthalene or naphthalenesulfonic acids with phenol and formaldehyde, polyoxyethylene octylphenol esters, ethoxylated isooctylphenol, ethoxylated octylphenol and ethoxylated nonylphenol, alkylphenol polyglycol ethers, tributylphenol polyglycol ethers, alkylaryl polyester alcohols, isotridecyl alcohols, fatty alcohol ethylene oxide condensates, ethoxylated castor oil, polyoxyethyene alkyl ethers, ethoxylated polyoxypropylene, lauryl alcohol polyglycol ether acetal, sorbitol esters, lignin, sulfite waste liquors and methyl cellulose.

Powders, dusts and broadcasting agents may be prepared by mixing or grinding the active ingredients with a solid carrier.

Granules, e.g., coated, impregnated or homogeneous granules, may be prepared by bonding the active ingredients to solid carriers. Examples of solid carriers are mineral earths such as silicic acid, silica gels, silicates, talc, kaolin, Attaclay, limestone, lime, chalk, bole, loess, clay, dolomite, diatomaceous earth, calcium sulfate, magnesium sulfate, magnesium oxide, ground plastics, fertilizers such as ammonium sulfate, ammonium phosphate, ammonium nitrate, and ureas and vegetable products such as grain flours, bark meal, wood meal, and nutshell meal, cellulosic powders, etc.

The formulations contain from 0.1 to 95, and preferably 0.5 to 90, % by weight of active ingredient.

EXAMPLE 5

90 parts by weight of compound 2 is mixed with 10 parts by weight of N-methyl-α-pyrrolidone. A mixture is obtained which is suitable for application in the form of very fine drops.

EXAMPLE 6

20 parts by weight of compound 8 is dissolved in a mixture consisting of 80 parts by weight of xylene, 10 parts by weight of the adduct of 8 to 10 moles of ethylene oxide to 1 mole of oleic acid-N-monoethanolamide, 5 parts by weight of the calcium salt of dodecylbenzenesulfonic acid, and 5 parts by weight of the adduct of 40 moles of ethylene oxide to 1 mole of castor oil. By pouring the solution into 100,000 parts by weight of water and uniformly distributing it therein, an aqueous dispersion is obtained containing 0.02% by weight of the active ingredient.

EXAMPLE 7

20 parts by weight of compound 13 is dissolved in a mixture consisting of 40 parts by weight of cyclohexanone, 30 parts by weight of isobutanol, 20 parts by weight of the adduct of 7 moles of ethylene oxide to 1 mole of isooctylphenol, and 10 parts by weight of the adduct of 40 moles of ethylene oxide to 1 mole of castor oil. By pouring the solution into 100,000 parts by weight of water and uniformly distributing it therein, an aqueous dispersion is obtained containing 0.02% by weight of the active ingredient.

EXAMPLE 8

20 parts by weight of compound 23 is dissolved in a mixture consisting of 25 parts by weight of cyclohexanol, 65 parts by weight of a mineral oil fraction having a boiling point between 210° and 280° C., and 10 parts by weight of the adduct of 40 moles of ethylene oxide to 1 mole of castor oil. By pouring the solution into 100,000 parts by weight of water and uniformly distributing it therein, an aqueous dispersion is obtained containing 0.02% by weight of the active ingredient.

EXAMPLE 9

20 parts by weight of compound 7 is well mixed with 3 parts by weight of the sodium salt of diisobutylnaphthalene-α-sulfonic acid. 17 parts by weight of the sodium salt of a lignin-sulfonic acid obtained from a sulfite waste liquor, and 60 parts by weight of powdered silica gel, and triturated in a hammer mill. By uniformly distributing the mixture in 20,000 parts by weight of water, a spray liquid is obtained containing 0.1% by weight of the active ingredient.

EXAMPLE 10

3 parts by weight of compound 46 is intimately mixed with 97 parts by weight of particulate kaolin. A dust is obtained containing 3% by weight of the active ingredient.

EXAMPLE 11

30 parts by weight of compound 2 is intimately mixed with a mixture consisting of 92 parts by weight of powdered silica gel and 8 parts by weight of paraffin oil which has been sprayed onto the surface of this silica gel. A formulation of the active ingredient is obtained having good adherence.

EXAMPLE 12

40 parts by weight of compound 7 is intimately mixed with 10 parts of the sodium salt of a phenolsulfonic acid-urea-formaldehyde condensate, 2 parts of silica gel and 48 parts of water to give a stable aqueous dispersion. Dilution in 100,000 parts by weight of water gives an aqueous dispersion containing 0.04 wt% of active ingredient.

EXAMPLE 13

20 parts of compound 8 is intimately mixed with 2 parts of the calcium salt of dodecylbenzenesulfonic acid, 8 parts of a fatty alcohol polyglycol ether, 2 parts of the sodium salt of a phenolsulfonic acid-urea-formaldehyde condensate and 68 parts of a paraffinic mineral oil. A stable oily dispersion is obtained. 

We claim:
 1. ##STR231## where R¹ and R² are identical or different and each denotes hydrogen, alkyl, alkoxyalkyl, or haloalkyl, R³ denotes unsubstituted alkyl, alkyl substituted by halogen, alkoxy, unsubstituted aryl or halogen-substituted aryl, unsubstituted or halogen-substituted alkenyl, unsubstituted or halogen- or alkoxy-substituted alkynyl, R⁴ denotes unsubstituted or alkyl-substituted cycloalkyl, bicycloalkyl, tricycloalkyl, phenyl with fused ring system, phenyl, or mono- or polysubstituted phenyl with the substitutents alkyl, haloalkyl, alkoxyalkyl, cycloalkyl, halogen, alkoxy, or haloalkoxy, with the provisio that R³ and R⁴ are different and W, X, Y and Z are identical or different and each denotes hydrogen, alkyl, haloalkyl, alkoxy, halogen, nitro and amino.
 2. A diurethane of the formula ##STR232## wherein R² is H or alkyl of 1-3 carbon atoms;R³ is alkyl of 1-4 carbon atoms, alkenyl of 2-4 carbon atoms or alkynyl of 3-4 carbon atoms; and R⁴ is cycloalkyl of 5-10 carbon atoms, unsubstituted phenyl or phenyl either mono- or poly-substituted by halogen, alkyl of 1-3 carbon atoms, or methoxy, the substituents on said substituted phenyl being identical or different. 